Catalysts & Ligands

Catalysts & Ligands Products Sold in Collaboration with Takasago

Ru-MACHO® SEGPHOS®

15, rue de l’Atome Zone Industrielle F-67800 BISCHHEIM (France) Tel.: +33 (0) 3 88 62 52 60 Fax: +33 (0) 3 88 62 26 81 Email: [email protected]

® Postfach 1215 DENEB RUCY D-77672 KEHL, Germany Tel.: +49 (0) 7851 75879 Fax: +33 (0) 3 88 62 26 81 Email: [email protected]

An Independent Distributor of Strem Chemicals Products Newton Hall, Town Street Newton, Cambridge, CB22 7ZE, UK Tel.: +44 (0)1223 873 028 Fax: +44 (0)1223 870 207 Email: [email protected] Strem Chemicals, Inc., established in 1964, is an employee-owned company that manufactures and markets specialty chemicals of high purity. Strem has been providing metal catalysts for synthetic organic chemistry research and fine chemical production for over fifty years.

Metal catalysts provide pathways to both chiral and achiral products. Our complete line of metal con- Catalysts & Ligands taining homogeneous catalysts and organocatalyst products are presented in this booklet. For many of Products Sold in Collaboration with Takasago these items, Strem is the first and only commercial supplier. Our licenses allow us to provide this technology for R&D and commercial applications. We have continued to add to this product line in order to Strem Chemicals is an ISO certified, employee- As part our biocatalyst prod- better serve our customers and allow them to achieve their research and commercial objectives. Many owned company that manufactures and markets uct line, of these items are also available in multi-kilogram quantities. specialty chemicals of high purity. We have been providing fine chemicals for research and commercial we currently offer enzymes, production for over fifty years. At Strem, we offer a including immobilized wide variety of catalysts, ligands, nanomaterials and CVD/ALD precursors. Most of our products are of enzymes, carriers, adsor- high purity, typically at 99%, while some are as high bents, chelating resins and a as 99.9999% metals purity. We continually seek to provide new technologies from around the globe to selection of add to our product line. We look forward to further advancements in order to best serve our customers’ needs with the quality and service they can trust from Strem. biocatalyst kits for screening of various processes. We We have licensing agreements with industry and academia, which allow easier access to continue patent-protected products for our customers. This booklet is comprised of our products which are sold in collaboration with Takasago International Corporation. to expand the scope of this About Takasago International Corporation category in order to better Takasago International Corporation was founded in Japan in 1920. For more than 95 years, Takasago has developed flavors and fragrances for some of the world’s most successful serve the enzymes for bio- food, beverage, fine fragrance, household and personal care products. Takasago isa catalytic development leading global company especially in the Asian region. fields. Takasago has vigorously pursued pharmaceutical intermediaries, functional materials, and other fine chemicals. Asymmetric synthesis, cultivated in their aroma ingredients development work, is a key technology of these products. By utilizing technology and their global network, they develop high-quality and innovative products that contribute to cultural and social progress. *** Our other booklets, which focus on applications and product classes, are available in print per request and also on our website. Below is a list of current booklet titles that are available. Please also check our Product Resources section online to find additional literature offerings, such as the Strem Chemiker, our technical publication, and product literature sheets. ▪ Biocatalysts ▪ Materials for Energy Applications ▪ Buchwald Ligands and Precatalysts ▪ Metal Catalysts for Organic Synthesis ▪ Carbon-Based Nanomaterials & ▪ Metal Organic Frameworks and Elemental Forms Ligands for MOF Synthesis ▪ Catalysts & Ligands Manufactured ▪ MOCVD, CVD & ALD Precursors Under License of Takasago Patent ▪ Nanomaterials ▪ Gold Elements & Compounds ▪ New Products ▪ Heterogeneous Catalysts ▪ Other Ligands ▪ High Purity Chiral Reagents - Sold in ▪ Phosphorous Ligands and Compounds Collaboration with Daicel ▪ Photocatalysts ▪ Kits ▪ PURATREM: High Purity Inorganics

[α]D ...... Specific rotation AAS ...... Atomic Absorption Standard ACS ...... Conforms to American Chemical Society specifications air sensitive ...... Product may chemically react with atmospheric oxygen or carbon dioxide at ambient conditions. Handle and store under an inert atmosphere of nitrogen or argon. amp ...... Ampouled b.p...... Boiling point in °C at 760mm, unless otherwise noted d...... Density dec...... Decomposes elec. gr...... Electronic Grade, suitable for electronic applications f.p...... Flash point in °F gran...... Granular heat sensitive ...... Product may chemically degrade if stored for prolonged periods of time at ambient temperatures or higher. Store at 5°C or lower. hydrate ...... Unspecified water content which may vary slightly from lot to lot hygroscopic ...... Product may absorb water if exposed to the atmosphere for prolonged periods of time (dependent on humidity and temperature). Handle and store under an inert atmosphere of nitrogen or argon. light sensitive ...... Product may chemically degrade if exposed to light liq...... Liquid m.p...... Melting point in °C moisture sensitive ...... Product may chemically react with water. Handle and store under an inert atmosphere of nitrogen or argon. NMR grade Suitable as a Nuclear Magnetic Resonance reference standard optical grade ...... For optical applications pwdr...... Powder primary standard ...... Used to prepare reference standards and standardize volumetric solutions PURATREM ...... Product has a minimum purity of 99.99% (metals basis) purified ...... A grade higher than technical, often used where there are no official standards P. Vol...... Pore volume pyrophoric ...... Product may spontaneously ignite if exposed to air at ambient conditions reagent ...... High purity material, generally used in the laboratory for detecting, measuring, examining or analyzing other substances REO ...... Rare Earth Oxides. Purity of a specific rare-earth metal expressed as a percentage of total rare-earths oxides. SA ...... Surface area store cold ...... Product should be stored at -18°C or 4°C, unless otherwise noted (see product details) subl...... Sublimes superconductor grade ...... A high purity, analyzed grade, suitable for preparing superconductors tech. gr...... Technical grade for general industrial use TLC ...... Suitable for Thin Layer Chromotography v.p...... Vapor pressure mm of Hg xtl...... Crystalline

About Purity

Chemical purity ...... is reported after the chemical name, e.g. Ruthenium carbonyl, 99% Metals purity ...... is reported in parentheses with the respective element, e.g. Gallium (III) bromide, anhydrous, granular (99.999%-Ga) PURATREM where 100% minus the metal purity is equal to the maximum allowable percentage of trace metal impurity

i NITROGEN (Compounds)

IRIDIUM (Compounds)

07-234507-2345 N-[(1R,2R)-2-Amino-1,2-diphenyl)ethyl]-2,4,6- Ph Ph 1g tris(1-methylethyl)benzenesulfonamide, 98% iPr 5g (R,R)-TipsDPEN (852212‑92‑1) O H2N N C29H38N2O2S; FW: 478.69; white to tan pwdr. S Note: Sold in collaboration with Takasago. H O iPr iPr

07-234607-2346 N-[(1S,2S)-2-Amino-1,2-diphenyl)ethyl]-2,4,6-tris(1-methylethyl) 1g benzenesulfonamide, 98% (S,S)-TipsDPEN (247923‑41‑7) 5g

C29H38N2O2S; FW: 478.69; white solid Note: Sold in collaboration with Takasago. PHOSPHORUS (Compounds)

15-006615-0066 (R)-(-)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl) t-Bu 250mg phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% OMe 1g (R)-(-)-DTBM-SEGPHOS® (566940‑03‑2) O 5g C74H100O8P2; FW: 1179.53; off‑white pwdr.; P t-Bu m.p. 126-128° O 2 Note: Sold in collaboration with Takasago. O P t-Bu Takasago SEGPHOS® Ligand Kit component. Technical Notes: O 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DTBM OMe SEGPHOS® ligand, as the ruthenium complex, gives superior t-Bu 2 enantioselectivity and diastereoselectivity through dynamic kinetic resolution in the asymmetric hydrogenation of a-substituted-β-ketoesters useful in the synthesis of carbapenum antibiotics.1 2. With rhodium, preferential enantioselective hydrogenation of more reactive olefin of extended enone structure.2 3. Rhodium catalyzed chemo-, regio, and entantioselective [2 + 2 + 2] cycloaddition of alkynes with isocyanates.3 4. With copper, enantioselective cross Aldol-type reaction of acetonitrile.4 5. With copper, enantioselective vinylsilane alkenylation of aldehydes.5 6. Gold carbene mediated stereoselective cyclopropanation of propargyl esters.6 7. With copper, enantioselective 1,2-reduction of ketones, and 1,4-reduction of a α,β-usaturated esters.7 8. With copper, catalytic enantioselective Mannich-type reaction.8 9. Enantioselective fluorination of b β-keto esters, tert-butoxycarbonyl lactones and lactmes with Sodeoka’s Pd- aqua complex and a fluorinating reagent.9 10. Rh-catalyzed intramolecular olefin or carbonyl hydroacylation.10 11. Pd-catalyzed γ-arylation of β,γ-unsaturated ketones. 12. Involved in numerous conjugate alkynylation, and ring-opening alkynylation of azabenzonorbornadienes.12 13. Involved in asymmetric hydroamination of bicyclic alkenes/dienes,13a diamination of conjugated dienes,13b and hydroalkoxylation/hydrosulfenylation of allenes.13c 14. Used in cycloaddition reactions such as 1,3-dipolar cycloaddition of azomethine ylides,14a and Au-catalyzed [2+2] cycoaddition of allenes.14b 15. Asymmetric conjugate addition of nitroalkanes to α,β-usaturated thioamides.15 16. Asymmetric synthesis of isothiazoles through Cu catalyzed conjugate addition of allyl cyanide to α,β- usaturated thioamides.16 17. Asymmetric Ag-catalyzed cycloadditions.17 18. Rhodium-catalyzed C–C bond cleavage to generate acyclic, asymmetric quaternary centers.18 19. Iridium-catalyzed intermolecular hydroamidation of olefins. 19,20 20. Palladium-Catalyzed Asymmetric Hydrogenation of α-Acyloxy-1-arylethanones O OH OTBS OAc CO CH CO CH 2 3 H2, Ru-(+)L 2 3 Tech. Note (1) Ref. (1) NH O NHCOC6H5 NHCOC6H5

1 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-0066 (R)-(-)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% (continued) (R)-(-)-DTBM-SEGPHOS® (566940‑03‑2)

Rh(COD)2, L, H2 Tech. Note (2) O O Ref. (2)

Cl Bz N [Rh(cod)2]BF4, L Cl + Tech. Note (3) Bz N Ref. (3)

O OH CuO-t-Bu, L Tech. Note (4) CN R H R Ref. (4)

O H HO Cu, L Tech. Note (5) + Si(OMe)3 F Ref. (5)

L(AuCl)2, AgSbF6 OPiv + Tech. Note (6) Ar Ar Ref. (6) OPiv

Cu-H, L O O O OH Tech. Note (7) Ref. (7b)

O O Cu, L PPh PPh HO2C CN 2 N 2 + HN Tech. Note (8) 2 3 Ref. (8) R R 1 CN 1 R R R2 R3

O 2+ - O NFSI, [LPd(OH2)2] 2TfO F Tech. Note (9) X CO2-t-Bu X CO2-t- Ref. (9a) Bu

O O Me Rh, L Tech. Note (10) R R Ref. (10) O O

NH2 O Me 1 O Br R2 Pd, L R + Tech. Note (11) N H Ref. (11) 2 H R1 Me R

Visit strem.com for new product announcements. 2 PHOSPHORUS (Compounds) 15-0066 (R)-(-)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% (continued) (R)-(-)-DTBM-SEGPHOS® (566940‑03‑2) TIPS O Rh(COD)2, L, H2 Rh, L Tech. Note (12) Tech. Note (2) + TIPS O Ref. (12a) O O Ref. (2) H R H R

R Ir, L R NHAr Tech. Note (13) + ArNH2 Cl Bz Ref. (13a) N [Rh(cod)2]BF4, L Cl R R + Tech. Note (3) Bz Ref. (3) N R R H O R Au, L R Tech. Note (14) X O OH X Ref. (14b) CuO-t-Bu, L Tech. Note (4) CN H Ar R H R Ref. (4) Ar

O OH OTBS O H HO OAc Cu, L CO CH CO CH Tech. Note (5) 2 3 H2, Ru-(+)L 2 3 Tech. Note (15) + Si(OMe)3 Ref. (5) Ref. (15) F NH O NHCOC6H5 NHCOC6H5

Bn2N L(AuCl)2, AgSbF6 Tech. Note (6) S OPiv + Ar Ar S N Ref. (6) S CN Cu, L Ph [O] OPiv + Bn2N Tech. Note (16) Ref. (16) Bn2N Ph Cu-H, L Ph O O O OH Tech. Note (7) Ref. (7b) CN

O O O MeO O R Ag, L BX2 Cu, L PPh2 Tech. Note (17) PPh2 HO2C CN HN Tech. Note (8) + N + X B OMe R N CO Me Ref. (17a) 2 3 Ref. (8) 2 2 R CO2Me R R 1 CN 1 R N R R R2 R3

Et OH Rh, L Et Me O O 2+ - O Tech. Note (18) NFSI, [LPd(OH2)2] 2TfO F Tech. Note (9) BnO Ref. (18) Ph X CO2-t-Bu X CO2-t- Ref. (9a) BnO Ph Bu O O O Ir, L O Me Tech. Note (19) + R NH Ar Ref. (19) Rh, L Tech. Note (10) Ar NH2 R R R Ref. (10) O O Ir, L Ar + R O Tech. Note (19) NH2 O Me Ar OH Ref. (20) 2 1 O R Br R Pd, L R + Tech. Note (11) N H Ref. (11) 2 H R1 Me R

3 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-0066 (R)-(-)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% (continued) (R)-(-)-DTBM-SEGPHOS® (566940‑03‑2)

O OH O tBu Pd(OCOCF3)2, 15-0066 O tBu Tech. Note (20) R R EtOH/TFE (4:1), 0C, H2 (30 Bar) Ref. (21) O O 24h, s/c = 50-50000 References: 1. Adv. Synth. Cat., 2001, 343, 264. 2. Chem. Eur. J. 2008, 14, 2060 3. Org. Lett., 2005, 7, 4737. 4. Org. Lett., 2005, 7, 3757. 5. J. Am. Chem. Soc., 2005, 127, 4138. 6. J. Am. Chem. Soc., 2005, 127, 18002. 7. (a) J. Am. Chem. Soc., 2004, 126, 8352. (b) Org. Lett., 2002, 4, 4045. 8. J. Am. Chem. Soc., 2009, 131, 9610. 9. (a) J. Am. Chem. Soc., 2002, 124, 14530. (b) J. Org. Chem., 2007, 72, 246. 10. J. Am. Chem. Soc., 2008, 130, 2916. 11. Angew. Chem. Int. Ed., 2008, 47, 177. 12. (a) Angew. Chem. Int. Ed., 2009, 48, 8057. (b) Org. Lett., 2008, 10, 4057. 13. (a) J. Am. Chem. Soc., 2008, 130, 12220. (b) Org. Lett., 2008, 10, 4231. (c) Chem. Commun., 2009, 3528. 14. (a) Angew. Chem. Int. Ed., 2009, 48, 340. (b) J. Am. Chem. Soc., 2007, 129, 12402. 15. Org. Lett., 2012, 14, 110. 16. Angew. Chem. In. Ed., 2011, 50, 7910. 17. (a) J. Org. Chem., 2011, 76, 1945. (b) J. Am. Chem. Soc., 2010, 132, 3263. 18. J. Am. Chem. Soc., 2010, 132, 5340. 19. J. Am. Chem. Soc., 2012, 134, 11960. 20. J. Am. Chem. Soc., 2013, 135, 9303. 21. J. Am. Chem. Soc., 2013, 135, 15746.

15-006715-0067 (S)-(+)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4’-bi-1,3- 250mg benzodioxole, min. 98% (S)-(+)-DTBM-SEGPHOS® (210169‑40‑7) 1g

C74H100O8P2; FW: 1179.53; off‑white pwdr.; m.p. 126-128° 5g Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ligand Kit component.

15-013615-0136 (R)-(+)-5,5’-Bis(diphenylphosphino)-4,4’-bi-1,3- O 250mg benzodioxole, min. 98% (R)-(+)-SEGPHOS® 1g (244261‑66‑3) 5g O C38H28O4P2; FW: 610.57; off‑white pwdr.; m.p. 168-172° PPh2 Note: Sold in collaboration with Takasago. Takasago PPh SEGPHOS® Ligand Kit component. O 2 Technical Notes: 1. Ligand for the practical enantioselective synthesis of axially chiral biaryl O diphosphonates and dicarboxylates. 2. Ligand in the Rhodium-catalyzed - highly enantio- and diastereoselective cotrimerization of alkenes and dialkyl acetylene dicarboxylates leading to furylcyclopropanes. 3. Ligand present in the Rhodium-catalyzed asymmetric hydroarylation of 3-pyrroline. 4. Ligand for the dynamic kinetic resolution in the Rh-catalyzed asymmetric arylation of phospholene oxides. Z E Me 1-5 mol% [Rh(cod)2]BF4 Me (R)-Segphos Me E Z + Me CH2Cl2, rt Me E Tech. Note (1) 1-3 h Ref. (1) E Me Z Z=O,NTs,NSO (4-BrC H ) 2 6 4 54-81% yield E= P(O)(OEt)2, CO2Et 98->99% ee

Visit strem.com for new product announcements. 4 PHOSPHORUS (Compounds) 15-0136 (R)-(+)-5,5’-Bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole, min. 98% (R)-(+)-SEGPHOS® (continued) (244261‑66‑3)

E O OH E 1-5 mol% [Rh(cod)2]BF4 t Pd(OCOCF3)2, 15-0066 E O Bu t (R)-Segphos or (R)-H8-BINAP RuCl3 O R O Bu Tech. Note (20) R1 + O R H H 2 O EtOH/TFE (4:1), 0C, H2 (30 Bar) Ref. (21) (CH2Cl)2, rt - 40°C NaIO4 1 CO2R Tech. Note (2) O R1 E 2 R E 24h, s/c = 50-50000 E OR Ref. (2) 91%, >99% ee (E = CO R2) up to 62% yield 2 1 2 References: up to >99% ee R = (CH2)3Br, R = Me 1. Adv. Synth. Cat., 2001, 343, 264. dr = >99:1 2. Chem. Eur. J. 2008, 14, 2060 3. Org. Lett., 2005, 7, 4737. [Rh(OH)(coe)2]2 4. Org. Lett., 2005, 7, 3757. SO2R (5.0 mol% Rh) 5. J. Am. Chem. Soc., 2005, 127, 4138. SO2R N (R)-segphos (5.5 mol%) 6. J. Am. Chem. Soc., 2005, 127, 18002. + (ArBO)3 N Tech. Note (3) 7. (a) J. Am. Chem. Soc., 2004, 126, 8352. (b) Org. Lett., 2002, 4, 4045. Ref. (3) R = 4-MeOC6H4 8. J. Am. Chem. Soc., 2009, 131, 9610. THF/H2O (10/1) Ar Ar = substituted phenyls 9. (a) J. Am. Chem. Soc., 2002, 124, 14530. (b) J. Org. Chem., 2007, 72, 246. 89-96% ee (R) 10. J. Am. Chem. Soc., 2008, 130, 2916. 11. Angew. Chem. Int. Ed., 2008, 47, 177. Rh/(R)-segphos 12. (a) Angew. Chem. Int. Ed., 2009, 48, 8057. (b) Org. Lett., 2008, 10, 4057. O R O R P (5.0 mol% Rh) high yield 13. (a) J. Am. Chem. Soc., , 130, 12220. (b) Org. Lett., , 10, 4231. (c) Chem. Commun., , 3528. P 2008 2008 2009 + ArB(pin) >97:3 dr 14. (a) Angew. Chem. Int. Ed., 2009, 48, 340. (b) J. Am. Chem. Soc., 2007, 129, 12402. KOH (10 equiv) Tech. Note (4) 94-99% ee Ref. (4) 15. Org. Lett., 2012, 14, 110. R = aryl, sec-alkyl dioxane/H2O (10/1) Ar 16. Angew. Chem. In. Ed., 2011, 50, 7910. 80°C, 16 h 17. (a) J. Org. Chem., 2011, 76, 1945. (b) J. Am. Chem. Soc., 2010, 132, 3263. 18. J. Am. Chem. Soc., 2010, 132, 5340. References: 19. J. Am. Chem. Soc., 2012, 134, 11960. 1. Org. Lett., 2008, 10, 2849. 20. J. Am. Chem. Soc., 2013, 135, 9303. 2. Org. Lett., 2008, 10, 2825. 21. J. Am. Chem. Soc., 2013, 135, 15746. 3. J. Am. Chem. Soc., 2013, 135, 10990. 4. J. Am. Chem. Soc., 2017, 139, 8122.

15-006715-0067 (S)-(+)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4’-bi-1,3- 250mg benzodioxole, min. 98% (S)-(+)-DTBM-SEGPHOS® (210169‑40‑7) 1g 15-013715-0137 (S)-(-)-5,5’-Bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole, min. 98% 250mg (S)-(-)-SEGPHOS® (210169‑54‑3) 1g C74H100O8P2; FW: 1179.53; off‑white pwdr.; m.p. 126-128° 5g Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ligand Kit C38H28O4P2; FW: 610.57; off‑white pwdr.; m.p. 168-172° 5g component. Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ligand Kit component. 15-013615-0136 (R)-(+)-5,5’-Bis(diphenylphosphino)-4,4’-bi-1,3- O 250mg Technical Note: benzodioxole, min. 98% (R)-(+)-SEGPHOS® 1g 1. See 15-0136 (page 4) (244261‑66‑3) 5g

O 15-015015-0150 (R)-(+)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% 250mg C38H28O4P2; FW: 610.57; off‑white pwdr.; m.p. 168-172° PPh2 Note: Sold in collaboration with Takasago. Takasago (R)-(+)-BINAP (76189‑55‑4) 1g PPh2 SEGPHOS® Ligand Kit component. O C44H32P2; FW: 622.70; white to off‑white pwdr.; 5g Technical Notes: m.p. 240.5-242° PPh2 Note: Sold in collaboration with Takasago. Takasago BINAP 1. Ligand for the practical enantioselective synthesis of axially chiral biaryl O PPh2 diphosphonates and dicarboxylates. Ligand Kit component. 2. Ligand in the Rhodium-catalyzed - highly enantio- and diastereoselective cotrimerization of alkenes and Technical Notes: dialkyl acetylene dicarboxylates leading to furylcyclopropanes. 1. (R)-BINAP or (R)-Tol-BINAP can be combined with dichloro(1,5- 3. Ligand present in the Rhodium-catalyzed asymmetric hydroarylation of 3-pyrroline. cyclooctadiene)ruthenium to form precursors to NOYORI CATALYST 4. Ligand for the dynamic kinetic resolution in the Rh-catalyzed asymmetric arylation of phospholene oxides. SYSTEMS. These systems exhibit very high catalytic activity and enantioselectivity in the hydrogenation of a wide range of substrates. NOYORI CATALYST SYSTEMS have been shown to effect highly enantioselective hydrogenation Z of functionalized ketones where the substituents are dialkylamino, hydroxy, siloxy, carbonyl, ester, amide or thioester. E Me 2. Useful ligand in asymmetric Heck processes. 1-5 mol% [Rh(cod)2]BF4 Me 3. Ligand employed in palladium-catalyzed asymmetric arylation of ketones. (R)-Segphos Me E Z + 4. Ligand employed in rhodium-catalyzed 1,4-additions to enones. Me CH2Cl2, rt Me E Tech. Note (1) 5. Ligand employed in palladium-catalyzed hydroamination of styrene derivatives. 1-3 h Ref. (1) 6. Ligand employed in silver-catalyzed asymmetric Sakuri-Hosomi allylation and Mukaiyama aldol reaction. E Me 7. Ligand employed in rhodium-catalyzed kinetic resolution of enynes. Z 8. Ligand employed in asymmetric rhodium-catalyzed hydroboration of cyclopropenes. Z=O,NTs,NSO (4-BrC H ) 2 6 4 54-81% yield 9. Ligand employed in silver-catalyzed a-hydroxylation of stannyl enol ethers. E= P(O)(OEt)2, CO2Et 98->99% ee 10. Ligand employed in palladium-catalyzed synthesis of chiral allenes. 11. Ligand for palladium-catalyzed enantioselective hetero Michael addition to form b-amino acid derivatives. 12. Ligand employed in rhodium-catalyzed asymmetric rearrangement of alkynyl alkenyl carbinols. 13. Ligand employed in rhodium-catalyzed 1,2-addition of aluminium organyl compounds to cyclic enones.

5 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-0150 (R)-(+)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% (R)-(+)-BINAP (76189‑55‑4) (continued) 14. Ligand employed in iridium-catalyzed transfer hydrogenative allylation of benzylic alcohols. 15. Ligand employed in rhodium-catalyzed asymmetric C-Si bond formation by conjugate silyl transfer using a Si-B linkage. 16. Ligand employed in the iridium-catalyzed asymmetric cyclopropane-mediated carbonyl allylation of primary alcohols. 17. Ligand employed in the nickel-catalyzed asymmetric α-arylation of tetralones. 18. Ligand employed in the copper-catalyzed asymmetric propargylation of ketones. 19. Ligand employed in the cobalt-catalyzed asymmetric reductive coupling of alkynes with alkenes. 20. Ligand employed in the rhodium-catalyzed asymmetric 1,4-addition of arylalanes on trisubstituted enones. 21. Ruthenium-catalyzed asymmetric hydrocyanation of imines. 22. Palladium-catalyzed asymmetric intermolecular cyclization.

MeO I OTIPS 1. 10% Pd2(dba)3 Me CHO O 23% (S)-BINAP MeO base, DMA O Tech. Note (2) N N Ref. (5) Me Me 2. 3 N HCl Me

NHAr

ArNH + 10% [(R)-BINAP]Pd(OTf)2 Me 2 Tech. Note (5) Ref. (9) F3C CF3 80% yield 81% ee

AgOTf/BINAP O OH OSi(OMe)3 KF * Me + PhCHO tBu * Ph tBu 18-crown-6 Tech. Note (6) Me Ref. (10) MeOH 84% yield >99/1 syn/anti 97% ee

AgOTf/BINAP KF OH Si(OMe) Tech. Note (6) 3 + PhCHO * 18-crown-6 Ph Ref. (10) MeOH

Me Me Me

[Rh(cod)Cl]2 BINAP + O O Tech. Note (7) O AgSbF Me Ref. (11) Me 6 Me O Me OH Me OH racemic 99% ee 99% ee

CO Me Me 2 CO Me O [Rh(cod)Cl] /BINAP * H Me 2 2 + B H B Tech. Note (8) O THF, rt OO Ref. (12)

96% yield, 94% ee

Visit strem.com for new product announcements. 6 PHOSPHORUS (Compounds) 15-0150 (R)-(+)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% (R)-(+)-BINAP (76189‑55‑4) (continued) 14. Ligand employed in iridium-catalyzed transfer hydrogenative allylation of benzylic alcohols. OSnBu3 O O 15. Ligand employed in rhodium-catalyzed asymmetric C-Si bond formation by conjugate silyl transfer using a Si-B linkage. AgClO4 O Ph OH Tech. Note (9) 16. Ligand employed in the iridium-catalyzed asymmetric cyclopropane-mediated carbonyl allylation of primary alcohols. N BINAP CuSO4 + N Ref. (13) 17. Ligand employed in the nickel-catalyzed asymmetric α-arylation of tetralones. Ph O H 18. Ligand employed in the copper-catalyzed asymmetric propargylation of ketones. THF MeOH 19. Ligand employed in the cobalt-catalyzed asymmetric reductive coupling of alkynes with alkenes. 20. Ligand employed in the rhodium-catalyzed asymmetric 1,4-addition of arylalanes on trisubstituted enones. EtO2C EtO2C CO2Et 21. Ruthenium-catalyzed asymmetric hydrocyanation of imines. CO2Et Pd2(dba)3/BINAP 22. Palladium-catalyzed asymmetric intermolecular cyclization. Ph + N O • HN Ac Tech. Note (10) H Br CsOtBu, CH Cl Ph Ref. (14) MeO I OTIPS 1. 10% Pd2(dba)3 Me CHO 2 2 O MeO Me 23% (S)-BINAP 75% yield, 89% ee base, DMA O Tech. Note (2) N N Ref. (5) MeO Me Me 2. 3 N HCl Me anisidine triflate O O [PdL(OH)2]2(OTf)2 NH O Me N O Tech. Note (11) NHAr O THF * Ref. (15) Me N O ArNH + 10% [(R)-BINAP]Pd(OTf)2 Me 2 Tech. Note (5) Ref. (9) 92% yield, 98% ee F3C CF3 80% yield SiMe2tBu 81% ee SiMe2tBu [Rh(OH)(cod)]2 BINAP HO O AgOTf/BINAP Me Tech. Note (12) O OH Ph Me Ref. (16) OSi(OMe)3 KF toluene * Ph Me + PhCHO tBu * Ph tBu 18-crown-6 Tech. Note (6) 91% yield, 98% ee Me Ref. (10) MeOH 84% yield O Me >99/1 syn/anti [{Rh(cod)OMe}2] OH 97% ee BINAP Tech. Note (13) AgOTf/BINAP AlMe3, THF Ref. (17) KF OH Si(OMe) Tech. Note (6) Me Me Me Me 3 + PhCHO * 18-crown-6 Ph Ref. (10) 86% yield, 99% ee MeOH OH [Ir(cod)Cl]2/BINAP OH Me Me Me Cs2CO3 OAc + Tech. Note (14) [Rh(cod)Cl]2 m-NO BzOH 2 Ref. (18) BINAP + CO2Me THF CO2Me O O Tech. Note (7) O AgSbF Me Ref. (11) Me 6 Me 77% yield, 93% ee O Me OH Me OH O Ph O racemic 99% ee 99% ee [Rh(cod)2]OTf/BINAP Me Si O Et3N F3C O + B F3C O CO Me Me Tech. Note (15) Me 2 O Ph 1,4-dioxane/H2O Ph SiMe Ph Ref. (19) CO Me O [Rh(cod)Cl] /BINAP * H 2 Me 2 2 + B H B Tech. Note (8) 65% yield, >99% ee O THF, rt OO Ref. (12)

96% yield, 94% ee

7 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-0150 (R)-(+)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% (R)-(+)-BINAP (76189‑55‑4) (continued)

CO2Me OH OH Ir cat. L CO2Me R R K3PO4, H2O Tech. Note (16) THF, 60 °C MeO2C Ref. (20) up to 99 % ee CO Me up to 20:1 dr 2

O O Ar R Ni cat. L R ArClH Tech. Note (17) NaOtBu, toluene Ref. (21) 60 °C up to 99 % ee

O OH TMS TMS Cu cat. L 1 Tech. Note (18) 1 2 R BPin R R LiOtBu, THF R2 Ref. (22) -62 °C, 18 h up to 98 % ee

O O R1 Co cat. L n Zn, ZnI2 n Tech. Note (19) R2 1 4 Ref. (23) 4 dioxane, H2O R 3 R 3 R 2 R R r.t., 24 h R up to 96 % ee

O O

Rh cat. L Tech. Note (20) ArAlMe2 dioxane, 6% THF Ref. (24) 5 °C, 15 h Ar up to 99 % ee

Cbz N HCN, Ru, L CbzHN CN Tech. Note (21) Ref. (25) R H R H

H O OTf O Pd, L Tech. Note (22) + H Ref. (26)

References: 1. CHEMTECH, 1992, 360. 2. Asymmetric Catalysis in Organic Synthesis, 1993, 61. 3. J. Am. Chem. Soc., 1988, 110, 629. 4. Science, 1990, 248, 1194. 5. J. Am. Chem. Soc., 1998, 120, 6477. 6. Encyclopedia of Reagents for Organic Synthesis, 1995, Vol. 1, 509. 7. J. Am. Chem. Soc., 1998, 120, 1918. 8. J. Am. Chem. Soc., 1998, 120, 5579. 9. J. Am. Chem. Soc., 2000, 122, 9546. 10. J. Org. Chem., 2003, 68, 5593. 11. J. Am. Chem. Soc., 2003, 125, 11472. 12. J. Am. Chem. Soc., 2003, 125, 7198.

Visit strem.com for new product announcements. 8 PHOSPHORUS (Compounds) 15-0150 (R)-(+)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% (R)-(+)-BINAP (76189‑55‑4) (continued) 13. J. Am. Chem. Soc., 2003, 125, 6038. CO2Me OH OH Ir cat. L 14. J. Am. Chem. Soc., 2001, 123, 2089. CO2Me R 15. (a) JP4446465B2, (b) Org. Lett. 2004, 6, 1861. K PO , H O R 3 4 2 Tech. Note (16) 16. J. Am. Chem. Soc., 2007, 129, 14158. MeO2C Ref. (20) THF, 60 °C 17. Angew. Chem. Int. Ed., 2007, 46, 7122. up to 99 % ee 18. J. Am. Chem. Soc., 2008, 130, 14891. CO2Me up to 20:1 dr 19. Angew. Chem. Int. Ed., 2008, 47, 3818. 20. J. Am. Chem. Soc., 2011, 133, 18618. O O 21. J. Am. Chem. Soc., 2011, 133, 16330. Ar 22. J. Am. Chem. Soc., 2011, 133, 10332. R Ni cat. L R ArClH Tech. Note (17) 23. J. Am. Chem. Soc., 2011, 133, 6942. NaOtBu, toluene Ref. (21) 24. Angew. Chem. Int. Ed., 2010, 49, 7769. 60 °C 25. Org. Lett., 2012, 14, 882. up to 99 % ee 26. Angew. Chem., Int. Ed., 2013, 52, 8676.

15-015115-0151 (S)-(-)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% (S)-(-)-BINAP 250mg O OH TMS (76189‑56‑5) 1g TMS Cu cat. L 1 Tech. Note (18) C44H32P2; FW: 622.70; white to off‑white pwdr.; m.p. 241-242° 5g 1 2 R BPin R R LiOtBu, THF R2 Ref. (22) Note: Sold in collaboration with Takasago. Takasago BINAP Ligand Kit component. -62 °C, 18 h Technical Note: up to 98 % ee 1. See 15-0150 (page 5)

15-297215-2972 (R)-(+)-2,2’-Bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’- 50mg O O octahydro-1,1’-binaphthyl (R)-(+)-H8-BINAP 250mg R1 Co cat. L (139139‑86‑9) PPh2 Zn, ZnI n C44H40P2; FW: 630.74; off‑white pwdr.; m.p. 207-208° 2 n 2 Tech. Note (19) PPh R 1 Note: Sold in collaboration with Takasago. 2 4 dioxane, H O R 4 Ref. (23) 3 R 2 3 R Technical Notes: R R2 R r.t., 24 h 1. Biaryl bisphosphine ligand. The H8-BINAP ligand, as the ruthenium up to 96 % ee complex, catalyzes hydrogenation of unsaturated carboxylic acids to a higher ee than does BINAP. (Ref. 1,2) O O 2. The ruthenium catalyzed hydrogenation of aryl propenoic acid to produce the drug Ibuprofen. 3. Rhodium catalyzed asymmetric regioselective 1,4-addition of arylboronic acids to 3-substituted maleimides. Rh cat. L 4. Ligand for palladium-catalyzed enantioselective hydrogenation of substituted indoles. ArAlMe Tech. Note (20) 2 Ref. (24) 5. Rhodium-catalyzed enantioselective cyclization of γ-alkynylaldehydes with acyl phosphonates. dioxane, 6% THF 6. Enantioselective synthesis of axially chiral 1-arylisoquinolines by Rh-catalyzed [2+2+2] cycloaddition. 5 °C, 15 h Ar up to 99 % ee 7. Enantioselective synthesis of 2,3-disubstituted indolines through Bronsted acid/Pd-complex-promoted tandem reactions. 8. Dehydration triggered asymmetric hydrogenation of 3-(α-hydroxyalkyl)indoles Cbz 9. Iridium-catalyzed [2+2+2] cycloaddition of α,ω-diynes with arylisocyanates N HCN, Ru, L CbzHN CN Tech. Note (21) Ref. (25) 10. Asymmetric hydrogenation of 3-(toluenesulfonamidoalkyl)-indoles R H R H 11. Asymmetric Rh(I)-catalyzed intramolecular [3+2] cycloaddition of 1-yne-vinylcyclopropanes for bicyclo[3.3.0] compounds with a chiral quaternary carbon stereocenter. H O 12. Enantioselective intermolecular [2+2+2] cycloadditions of ene-allenes with allenoates. 13. Rh-catalyzed one-pot intermolecular [2+2+2] trimerization/asymmetric intramolecular [4+2] cycloaddition of OTf O Pd, L Tech. Note (22) two aryl ethynyl ethers and 5-alkynals. + H Ref. (26) 14. Rh-catalyzed regio-, diastereo-, and enantioselective [2+2+2] cycloaddition of 1,6-enynes with acrylamides.

References: 1. CHEMTECH, 1992, 360. 2. Asymmetric Catalysis in Organic Synthesis, 1993, 61. 3. J. Am. Chem. Soc., 1988, 110, 629. Tech. Note (1,2) 0.5 mol% [(S)-L]Ru(OAc) 4. Science, 1990, 248, 1194. 2 Ref. (1,2) 5. J. Am. Chem. Soc., 1998, 120, 6477. 6. Encyclopedia of Reagents for Organic Synthesis, 1995, Vol. 1, 509. 100 atm H2, MeOH, 8 h, rt COOH 7. J. Am. Chem. Soc., 1998, 120, 1918. COOH 8. J. Am. Chem. Soc., 1998, 120, 5579. 97%, 97% ee 9. J. Am. Chem. Soc., 2000, 122, 9546. 10. J. Org. Chem., 2003, 68, 5593. 11. J. Am. Chem. Soc., 2003, 125, 11472. 12. J. Am. Chem. Soc., 2003, 125, 7198.

9 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-2972 (R)-(+)-2,2’-Bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl

(continued) (R)-(+)-H8-BINAP (139139‑86‑9) O O

2.5 mol% [RhCl(C2H4)2]2 2.75 mol% (R)-H8-Binap, KOH NBn NBn + PhB(OH)2 Tech. Note (3) Et Ref. (3) Et dioxane/H2O 10:1, 3h, 50° Ph O O 87%, >97%ee

R2 R2 2.0 mol% Pd(OTFA)2 2.4 mol% (R)-H8-Binap R1 R3 R1 R3 Tech. Note (4) N L-CSA, H2 (700 psi) N Ref. (4) H H CH2Cl2/TFE (1/1), rt 84–96% ee

O [Rh(cod)2]BF4 H O O L R3 1 + Z O Tech. Note (5) R 3 2) 2 R P(O)(OR P(O)(OR )2 Ref. (5) Z 2 CH2Cl2, 80 °C 5h R1

1 R Z Me R2 [Rh(cod)2]BF4 Me L Tech. Note (6) Me R1 Ref. (6) Z + N 2 CH2Cl2, 80 °C R Me 16h N

Tech. Note (7) 0.5 mol% [(S)-L]Ru(OAc)2 Ref. (7)

100 atm H2, MeOH, 8 h, rt COOH COOH 97%, 97% ee

HO R3 R3 Pd(OTFA)2

1 2 L 1 2 Tech. Note (8) R R R R Ref. (8) N TsOH-H2O, H2 N H H CH2Cl2/TFE (2:1), 50 °C

[Ir(cod)Cl]2 MeO2C Me + L MeO2C N Tech. Note (9) N benzene, reflux MeO C OMe Ref. (9) MeO2C Me C OMe 2 O O

Visit strem.com for new product announcements. 10 PHOSPHORUS (Compounds) 15-2972 (R)-(+)-2,2’-Bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl

(continued) (R)-(+)-H8-BINAP (139139‑86‑9) O O TsHN R3 R3 2.5 mol% [RhCl(C2H4)2]2 Pd(OTFA)2 2.75 mol% (R)-H8-Binap, KOH NBn L NBn + PhB(OH)2 Tech. Note (3) Tech. Note (10) R2 R2 Ref. (3) Ref. (10) Et N Et dioxane/H2O 10:1, 3h, 50° Ph N TsOH-H2O, H2 O H H O R CH2Cl2/TFE (1:1), 50 °C R1 87%, >97%ee 1

[Rh(CO)2Cl]2 2 2 R R R AgSbF6 2.0 mol% Pd(OTFA)2 R L Tech. Note (11) 2.4 mol% (R)-H8-Binap X X Ref. (11) R1 R3 R1 R3 Tech. Note (4) DCE N L-CSA, H2 (700 psi) N Ref. (4) H H CH2Cl2/TFE (1/1), rt Ar [Rh(C2H4)2Cl]2 84–96% ee Ar CO2Et AgOTf MeO2C CO2Et MeO2C EtO2C + L Tech. Note (12) O CO2Me O [Rh(cod)2]BF4 H EtO C Ref. (12) O MeO2C toluene, 100 °C 2 L R3 H 1 + Z O Tech. Note (5) R 3 2) 2 R P(O)(OR P(O)(OR )2 Ref. (5) Z 2 CH2Cl2, 80 °C 5h 1 R O H OAr [Rh(cod)2]BF4 OAr L 1 2 + Z H Z Tech. Note (13) R Z OAr Ref. (13) R (CH2Cl)2, 80 °C Me R2 [Rh(cod)2]BF4 R O Me L Tech. Note (6) N Me R1 Ref. (6) 1 Z + R2 R O CH2Cl2, 80 °C 1 O [Rh(cod) ]BF Me R 2 4 R3 16h N + R3 L N Tech. Note (14) Z N Z R4 Ref. (14) 4 CH Cl , r.t 2 R 2 2 R2 R 16h References: 1. J. Org. Chem., 1996, 61, 5510. 2. Topics Organometal. Chem. 2004, 6, 63 (review). 3. J. Am. Chem. Soc., 2006, 128, 5628. Tech. Note (7) 0.5 mol% [(S)-L]Ru(OAc)2 4. J. Am. Chem. Soc., 2010. 132, 8909. Ref. (7) 5. J.Am.Chem. Soc. 2011, 133, 6918. 6. Chem. Eur. J. 2011, 17, 1428. 100 atm H2, MeOH, 8 h, rt COOH 7. Chem. Eur. J. 2011, 17, 7193. COOH 8. Chem. Sci., 2011, 2, 803. 97%, 97% ee 9. J. Org. Chem., 2012, 77, 908. 10. Org. Biomol. Chem., 2012, 10, 1235. HO 11. J. Am. Chem. Soc., 2012, 134, 398. R3 R3 Pd(OTFA)2 12. Org. Lett., 2012, 14, 6096. 13. Org. Lett., 2012, 14, 5856. 1 2 L 1 2 Tech. Note (8) R R R R Ref. (8) 14. Angew. Chem. Int. Ed., 2012, 51, 13031. N TsOH-H2O, H2 N H H 15-297315-2973 (S)-(-)-2,2’-Bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1’- 50mg CH2Cl2/TFE (2:1), 50 °C binaphthyl (S)-(-)-H8-BINAP (139139‑93‑8) 250mg

C44H40P2; FW: 630.74; off‑white pwdr.; m.p. 207-208° Note: Sold in collaboration with Takasago. [Ir(cod)Cl]2 Technical Note: MeO2C Me L MeO C + 2 N Tech. Note (9) 1. See 15-2972 (page 9) N benzene, reflux MeO C OMe Ref. (9) MeO2C Me C OMe 2 O O

11 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds)

15-015215-0152 (R)-(+)-2,2’-Bis(di-p-tolylphosphino)-1,1’- 250mg binaphthyl, 98% (R)-(+)-TolBINAP (99646‑28‑3) 1g

C48H40P2; FW: 678.79; white pwdr.; m.p. 255-257° P(p-tolyl)2 5g Note: Sold in collaboration with Takasago. Takasago BINAP Ligand Kit component. P(p-tolyl)2 Technical Notes: 1. See 15-0150. 2. Useful ligand for palladium-catalyzed carbon-oxygen bond formation. 3. Ligand for palladium-catalyzed α-arylation of ketones. 4. Ligand for Cu-catalyzed asymmetric conjugate reduction. 5. Ligand for Cu-catalyzed asymmetric dienolate addition to aldehydes. 6. Enantioselective conjugate reduction of lactones and lactams. 7. Ligand used in the enantioselective cycloaddition of allenylsilanes with α-Imino esters. 8. Catalytic Aldol reaction to ketones. 9. Ligand with rhodium catalyses [2+2+2] cycloaddition reaction of alkenes and alkynes. 10. Ligand used in the copper-catalyzed asymmetric conjugate addition of alkyl Grignard reagents on α,β- unsaturated esters. 11. Ligand used in the copper-catalyzed asymmetric synthesis of cyclopropanes via tandem conjugate addition and intramolecular enolate trapping.

( ) OH Pd(OAc)2 (5 mol%), tol-BINAP (6 mol%) n O R' Tech. Note (2) R' R o R Ref. (1) Br K2CO3, 100 C ( )n

1.5 mol% O O Pd2(dba)3 t-Bu Br + t-Bu Tech. Note (3) 3.6 mol% Ref. (2) tol-BINAP NaO-t-Bu

O 5% CuCl, 5% NaO-t-Bu, O 5% (S)-p-tol-BINAP

1.05 eq. PMHS, 0o C Tech. Note (4) CH2CH2Ph CH2CH2Ph Ref. (3)

86%, 94% ee

2% (S)-p-tol-BINAP CuF2 Me Me THF, -78o C Me Me OO OH OO PhCHO + Tech. Note (5) OSiMe3 Ph O Ref. (4)

92%, 94% ee

. O CuCl2 H2O, (S)-p-Tol-BINAP O t-BuONa, PMHS O O Tech. Note (6) Toluene, i-PrOH Ref. (5) Bu -20o C Bu

(R)-Tol-BINAP Ts Ts OMe OMe [Cu(MeCN)4]BF4 Tech. Note (7) N N SiMe3 + Ref. (6) SiMe 3 EtO2C THF, MS4A EtO2C

Visit strem.com for new product announcements. 12 PHOSPHORUS (Compounds)

15-015215-0152 (R)-(+)-2,2’-Bis(di-p-tolylphosphino)-1,1’- 250mg 15-0152 (R)-(+)-2,2’-Bis(di-p-tolylphosphino)-1,1’-binaphthyl, 98% (R)-(+)-TolBINAP (99646‑28‑3) binaphthyl, 98% (R)-(+)-TolBINAP (99646‑28‑3) 1g (continued) C H P ; FW: 678.79; white pwdr.; m.p. 255-257° P(p-tolyl) 5g 48 40 2 2 1) CuF 3PPh3 2EtOH Note: Sold in collaboration with Takasago. Takasago (S)-p-Tol-BINAP BINAP Ligand Kit component. P(p-tolyl) 2 OTMS Technical Notes: OH O O Tech. Note (8) 1. See 15-0150. Ph OMe , (EtO)3SiF Me 2. Useful ligand for palladium-catalyzed carbon-oxygen bond formation. Me Me OMe Ref. (7) 3. Ligand for palladium-catalyzed α-arylation of ketones. o Me THF, -20 C, 24 h Ph 4. Ligand for Cu-catalyzed asymmetric conjugate reduction. . 5. Ligand for Cu-catalyzed asymmetric dienolate addition to aldehydes. 2) 3HF NEt3 99%, 82% ee 6. Enantioselective conjugate reduction of lactones and lactams. 7. Ligand used in the enantioselective cycloaddition of allenylsilanes with α-Imino esters. OMe 8. Catalytic Aldol reaction to ketones. 10 mol% 9. Ligand with rhodium catalyses [2+2+2] cycloaddition reaction of alkenes and alkynes. 10. Ligand used in the copper-catalyzed asymmetric conjugate addition of alkyl Grignard reagents on α,β- [Rh(cod)2]BF4, L, OMe unsaturated esters. TsN + TsN Tech. Note (9) 11. Ligand used in the copper-catalyzed asymmetric synthesis of cyclopropanes via tandem conjugate addition DCE, 12h 60° * OMe Ref. (8) and intramolecular enolate trapping. 81% 97% ee ( )n OH Pd(OAc)2 (5 mol%), tol-BINAP (6 mol%) OMe O R' Tech. Note (2) R' R o R Ref. (1) Br K2CO3, 100 C ( )n O Cu cat. L R' O R'MgBr Tech. Note (10) OMe OMe 1.5 mol% R t-BuOMe, -40 °C R Ref. (9) O O Pd2(dba)3 up to 94 % ee t-Bu Br + t-Bu Tech. Note (3) 3.6 mol% Ref. (2) O Cu cat. L O tol-BINAP 2 2 Cl R MgBr R 1 Tech. Note (11) NaO-t-Bu R1 R t-BuOMe/CH2Cl2 Ref. (10) up to 98 % ee O 5% CuCl, 5% NaO-t-Bu, O 4 h, -78 °C to r.t. 5% (S)-p-tol-BINAP References: 1. J. Am. Chem. Soc., 1996, 118, 10333. o Tech. Note (4) 1.05 eq. PMHS, 0 C 2. J. Am. Chem. Soc., 1997, 119, 11108. Ref. (3) CH2CH2Ph CH2CH2Ph 3. J. Am. Chem. Soc., 2000, 122, 6797. 4. J. Am. Chem. Soc., 1998, 120, 837. 86%, 94% ee 5. J. Am. Chem. Soc., 2003, 125, 11253. 6. Org. Lett., 2003, 5(20), 3691. 7. J. Am. Chem. Soc., 2003, 125, 5644. 2% (S)-p-tol-BINAP CuF 2 8. Org. Lett., 2005, 7(22), 4955. Me Me o Me Me THF, -78 C 9. Chem. Commun., 2010, 46, 8694. OO OH OO PhCHO + Tech. Note (5) 10. J. Am. Chem. Soc., 2010, 132, 14349.

OSiMe3 Ph O Ref. (4) 15-015315-0153 (S)-(-)-2,2’-Bis(di-p-tolylphosphino)-1,1’-binaphthyl, 98% (S)-(-)-TolBINAP 250mg (100165‑88‑6) 1g

92%, 94% ee C48H40P2; FW: 678.79; white pwdr.; m.p. 255-257° 5g Note: Sold in collaboration with Takasago. Takasago BINAP Ligand Kit component. . Technical Notes: O CuCl2 H2O, (S)-p-Tol-BINAP O 1. See 15-0150. t-BuONa, PMHS 2. Useful ligand for palladium-catalyzed carbon-oxygen bond formation. O O Tech. Note (6) Ref. (5) 3. Ligand for palladium-catalyzed α-arylation of ketones. Toluene, i-PrOH 4. Ligand for Cu-catalyzed asymmetric conjugate reduction. Bu -20o C Bu 5. Ligand for Cu-catalyzed asymmetric dienolate addition to aldehydes. 6. Enantioselective conjugate reduction of lactones and lactams. (R)-Tol-BINAP 7. Ligand used in the enantioselective cycloaddition of allenylsilanes with α-Imino esters. Ts Ts OMe 8. Catalytic Aldol reaction to ketones. OMe [Cu(MeCN)4]BF4 Tech. Note (7) N N SiMe3 9. Ligand with rhodium catalyses [2+2+2] cycloaddition reaction of alkenes and alkynes. + Ref. (6) SiMe 10. Ligand used in the iridium-catalyzed enantioselective C-H bond activation of 2-(alkylamino)-pyridine with 3 EtO2C THF, MS4A EtO2C alkenes. 11. Iridium-catalyzed regio-, diastereo-, and enantioselective tert-(hydroxyl)-prenylation of alcohols. 12. Rhodium-catalyzed cross cyclotrimerization.

13 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-0153 (S)-(-)-2,2’-Bis(di-p-tolylphosphino)-1,1’-binaphthyl, 98% (S)-(-)-TolBINAP (100165‑88‑6) (continued)

( ) OH Pd(OAc)2 (5 mol%), tol-BINAP (6 mol%) n O R' Tech. Note (2) R' R o R Ref. (1) Br K2CO3, 100 C ( )n

1.5 mol% O O Pd2(dba)3 t-Bu Br + t-Bu Tech. Note (3) 3.6 mol% Ref. (2) tol-BINAP NaO-t-Bu

O 5% CuCl, 5% NaO-t-Bu, O 5% (S)-p-tol-BINAP

1.05 eq. PMHS, 0o C Tech. Note (4) CH2CH2Ph CH2CH2Ph Ref. (3)

86%, 94% ee

2% (S)-p-tol-BINAP CuF2 Me Me THF, -78o C Me Me OO OH OO PhCHO + Tech. Note (5) OSiMe3 Ph O Ref. (4)

92%, 94% ee

. O CuCl2 H2O, (S)-p-Tol-BINAP O t-BuONa, PMHS O O Tech. Note (6) Toluene, i-PrOH Ref. (5) Bu -20o C Bu

(R)-Tol-BINAP Ts Ts OMe OMe [Cu(MeCN)4]BF4 Tech. Note (7) N N SiMe3 + Ref. (6) SiMe 3 EtO2C THF, MS4A EtO2C

1) CuF 3PPh3 2EtOH (S)-p-Tol-BINAP OTMS OH O O Tech. Note (8) Ph OMe , (EtO)3SiF Me Me Me OMe Ref. (7) Me THF, -20o C, 24 h Ph . 2) 3HF NEt3 99%, 82% ee

OMe 10 mol% [Rh(cod)2]BF4, L, OMe TsN + TsN Tech. Note (9) DCE, 12h 60° * OMe Ref. (8)

81% 97% ee OMe

Visit strem.com for new product announcements. 14 PHOSPHORUS (Compounds) 15-0153 (S)-(-)-2,2’-Bis(di-p-tolylphosphino)-1,1’-binaphthyl, 98% (S)-(-)-TolBINAP (100165‑88‑6) (continued)

( ) OH Pd(OAc)2 (5 mol%), tol-BINAP (6 mol%) R2 n O R' Tech. Note (2) R' R o ( ) R Ref. (1) N R2 N Br K2CO3, 100 C n Ir cat. L Tech. Note (10) N R1 DME, 75-95 °C N R1 Ref. (9) H H 1.5 mol% up to 90 % ee O O Pd2(dba)3 t-Bu Br + t-Bu Tech. Note (3) OH 3.6 mol% Ref. (2) OH Ir, L tol-BINAP + R Tech. Note (11) R O Me Me Ref. (10) NaO-t-Bu OH

O 5% CuCl, 5% NaO-t-Bu, O O O Si(R)3 R1 5% (S)-p-tol-BINAP R Rh, L (R)3Si R4 + + N 3 N Tech. Note (12) o Tech. Note (4) R R4 Ref. (11) 1.05 eq. PMHS, 0 C 4 EtO2C Ref. (3) CO2Et CH2CH2Ph CH2CH2Ph R1 References: 86%, 94% ee 1. J. Am. Chem. Soc., 1996, 118, 10333 2. J. Am. Chem. Soc., 1997, 119, 11108 3. J. Am. Chem. Soc., , 122, 6797 2% (S)-p-tol-BINAP CuF 2000 2 4. J. Am. Chem. Soc., , 120, 837 Me Me o Me Me 1998 THF, -78 C 5. J. Am. Chem. Soc., 2003, 125, 11253 PhCHO + OO OH OO Tech. Note (5) 6. Org. Lett., 2003, 5, 20, 3691 OSiMe3 Ph O Ref. (4) 7. J. Am. Chem. Soc., 2003, 125, 5644 8. Org. Lett., 2005, 7, 22, 4955 92%, 94% ee 9. Org. Lett., 2011, 13, 4692 10. J. Am. Chem. Soc., 2014, 136, 8911 11. Angew. Chem., Int. Ed., 2014, 53, 2956 . CuCl2 H2O, (S)-p-Tol-BINAP O O 15-047815-0478 (R)-(+)-5,5’-Bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- Me 250mg t-BuONa, PMHS benzodioxole, min. 98% (R)-(+)-DM-SEGPHOS® 1g O O Tech. Note (6) Toluene, i-PrOH Ref. (5) (850253‑53‑1) O 5g o C46H44O4P2; FW: 722.79; off white to pale yellow pwdr.; Bu -20 C Bu O P Me m.p. 256-261° 2 Note: Sold in collaboration with Takasago. Takasago O (R)-Tol-BINAP SEGPHOS® Ligand Kit component. P Me OMe Ts Ts Technical Notes: O OMe [Cu(MeCN)4]BF4 Tech. Note (7) N N SiMe3 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM- + Ref. (6) SiMe3 SEGPHOS ligand, as the ruthenium complex, gives superior Me EtO2C THF, MS4A 2 EtO2C enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of α-substituted-β-ketoesters. See 15-0066. 1) CuF 3PPh3 2EtOH 2. Copper catalyzed enantioselective [3 + 2] cycloaddition as a route to γ–amino ketones and 3-pyrrolidinones. (S)-p-Tol-BINAP 3. Palladium catalyzed enantioselective addition of malonates to dihydroisoquinolines. OTMS 4. Ruthenium catalyzed enantioselective synthesis of β amino acids by hydrogenation. OH O 5. Ruthenium catalyzed asymmetric hydrogenation of 3-quinuclidinone. See 44-0098 for Ru catalyst. O Tech. Note (8) Ph OMe , (EtO)3SiF Me 6. Diastereo- and enantioselective ruthenium-catalyzed hydrohydroxyalkylation of 2-silyl-butadienes. Me Me OMe Ref. (7) 7. Asymmetric [2+2+2] cycloaddition. Me THF, -20o C, 24 h Ph 8. Linear selective C-H activation. 9. Ligand used in the asymmetric hydrogenation of quinoxalines, benzoxazines and Benzothiazine. . 2) 3HF NEt3 99%, 82% ee CH Ts 3 Ts 10 mol% OMe N Si(t-Bu)Me N [Cu(MeCN) ]BF / EtO2C 10 mol% 2 + 4 4 * (+)L; Bz, reflux, 3h Tech. Note (2) [Rh(cod)2]BF4, L, Ref. (1) OMe EtO2C H TsN + TsN Tech. Note (9) Si(t-Bu)Me * OMe Ref. (8) 2 DCE, 12h 60° 90%, 75% ee

81% 97% ee OMe

15 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-0478 (R)-(+)-5,5’-Bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% (continued) (R)-(+)-DM-SEGPHOS® (850253‑53‑1) OMe

OMe 1) (Boc)2O MeO MeO 2) H2C(CO2R)2 (+L)Pd(OH2)2(OTf)2 NH Tech. Note (3) Ref. (2) N 1h, 0°, CH2Cl2

RO2C CO2R 92%, 97%ee

O O 0.1 mol% [RuCl2(p-cymene)]2 NH2 O 0.2 mol% L, NH4OAc, dioxane, Tech. Note (4) OCH3 H2 30 atm. 85°, 8 h OCH3 Ref. (3) 87%, 94% ee

0.1% (LRuCyCl)+Cl-, O 0.4% (R)-DAIPEN OH Tech. Note (5) + H N 2 IPA/t-BuOK N Ref. (4) 30 Atm, 30° 15 hr 99%, 91% ee

SiPhMe2 OH OMe RuHCl(CO)(PPh3)3 (5 mol %) Me2PhSi OH OMe + (R)-DM-SEGPHOS (5 mol %) o Tech. Note (6) PhMe (2 M), 95 C, 48h Ref. (5) 2 eq 1 eq 84 % (90 % ee) syn:anti > 20:1

Bu Bu

+ O Rh(I)/L O Tech. Note (7) Ref. (6)

Bu Bu

[Ir(cod)2]BF4/L Ph + Tech. Note (8) Ph N DME, 75 °C N Ref. (7) Ac Ac

H 2 X2 N X N H2, Ru-cat. L Tech. Note (9) t-C H OK 1 X1 N R 4 9 X N * R Ref. (8) H 96 to >99% ee

Visit strem.com for new product announcements. 16 PHOSPHORUS (Compounds) 15-0478 (R)-(+)-5,5’-Bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% (continued) (R)-(+)-DM-SEGPHOS® (850253‑53‑1) OMe References: 1. Org. Lett., 2005, 7, 1051. OMe 1) (Boc)2O MeO 2. J. Am. Chem. Soc., 2006, 128, 14010. 3. US.Pat. 7626034. 2) H2C(CO2R)2 MeO 4. (a) US.Pat. 7462722. (b) Org. Process Res. Dev. 2011, 15, 1130. (+L)Pd(OH2)2(OTf)2 NH Tech. Note (3) Ref. (2) 5. J. Am. Chem. Soc., 2011, 133, 10582. N 1h, 0°, CH2Cl2 6. J. Am. Chem. Soc., 2012, 134, 4080. 7. J. Am. Chem. Soc., 2012, 134, 17474. RO2C CO2R 8. Adv. Synth. Catal., 2013, 355, 2769. 92%, 97%ee 15-047915-0479 (S)-(-)-5,5’-Bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% 250mg (S)-(-)-DM-SEGPHOS® (210169‑57‑6) 1g O O 0.1 mol% [RuCl2(p-cymene)]2 NH2 O C46H44O4P2; FW: 722.79; off‑white to pale yellow pwdr.; m.p. 256-261° 5g Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ligand Kit 0.2 mol% L, NH4OAc, dioxane, Tech. Note (4) OCH component. 3 H2 30 atm. 85°, 8 h OCH3 Ref. (3) Technical Note: 87%, 94% ee 1. See 15-0478 (page 15)

15-047615-0476 (R)-(+)-2,2’-Bis[di(3,5-xylyl)phosphino]-1,1’- Me 250mg 0.1% (LRuCyCl)+Cl-, binaphthyl, 98% (R)-(+)-XylBINAP (137219‑86‑4) 1g O 0.4% (R)-DAIPEN OH C52H48P2; FW: 734.90; white to pale yellow xtl.; 5g Tech. Note (5) + H m.p. 203-206° N 2 IPA/t-BuOK N Ref. (4) P Me Note: Sold in collaboration with Takasago. 2 30 Atm, 30° 15 hr Takasago BINAP Ligand Kit component. 99%, 91% ee P Technical Notes: Me 1. See 15-0150. SiPhMe2 OH OMe RuHCl(CO)(PPh3)3 (5 mol %) Me2PhSi OH OMe 2. See 15-0477. 3. Ligand used in copper-catalyzed asymmetric Mannich-type Me + (R)-DM-SEGPHOS (5 mol %) 2 o Tech. Note (6) reactions of N-acylimino esters. PhMe (2 M), 95 C, 48h Ref. (5) 4. Ligand used in the enantioselective fluorination of oxindoles. 2 eq 1 eq 84 % (90 % ee) 5. Ligand used in [2+2+2] cycloaddition of tetraynes and hexaynes. syn:anti > 20:1 6. Ligand used in the asymmetric reduction of ketone via ruthenium-catalyzed asymmetric hydrogenation. 7. Asymmetric hydroboration of unsaturated imines. O Nu O Nu Bu EtO EtO * N Ph N Ph Tech. Note (3) Cu - cat./ L Bu H Ref. (1) O (10 mol%) O 76-81% Yield, 79-97% ee + O Rh(I)/L O Tech. Note (7) Ref. (6) Ph Ph F Bu Bu catalyst O O Tech. Note (4) Ref. (2) N NFSI N Boc Boc

[Ir(cod)2]BF4/L Ph Ar O + Tech. Note (8) Ph O N DME, 75 °C N Ref. (7) Ac Ac O O [IrCl(cod)]2, L Ar H Tech. Note (5) X2 N X2 N xylene, rt Ar H2, Ru-cat. L O Ref. (3) Tech. Note (9) O t-C H OK 1 X1 N R 4 9 X N * R Ref. (8) O H Ar 96 to >99% ee O 52-78% Yield, >90% ee

17 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-0476 (R)-(+)-2,2’-Bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl, 98% (R)-(+)-XylBINAP (137219‑86‑4) (continued)

O H2, (S)-RUCY-XylBINAP (44-0218) OH Tech. Note (6) R1 R2 2-propanol, 6-21 h R1 R2 Ref. (4) R1 = Ph, R2 = Me: >99% ee (R)

1) CuCl/L Ph B2Pin2, NaOtBu OH Ph THF/MeOH Tech. Note (7) Ph N Ph Ph N Ph Ref. (5) 2) reduction H 3) oxidation References: 1. J. Am. Chem. Soc., 2003, 125, 2507. 2. J. Am. Chem. Soc., 2005, 127, 10164 3. Tetrahedron, 2008, 64, 821. 4. J. Am. Chem. Soc., 2011, 133, 10696. 5. Org. Lett., 2013, 15, 4810.

15-047715-0477 (S)-(-)-2,2’-Bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl, 98% (S)-(-)-XylBINAP 250mg (135139‑00‑3) 1g

C52H48P2; FW: 734.90; white to pale yellow xtl.; m.p. 203-206° 5g Note: Sold in collaboration with Takasago. Takasago BINAP Ligand Kit component. Technical Note: 1. See 15-0476 (page 17)

15-100515-1005 Di-t-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl) Ph Me 250mg phosphine cBRIDP (742103‑27‑1) 1g C24H33P; FW: 352.49; white to pale yellow solid 5g air sensitive, (store cold) Ph P(tBu)2 Note: Sold in collaboration with Takasago. US7129367B2. Technical Notes: 1. Ligand effective for many classes of palladium-catalyzed coupling of aryl halides, including the Miyaura- Suzuki, Buchwald-Hartwig, Sonogashira, Heck, aryl etherification, and carbonylation reactions. 2. Ligand used in the palladium catalyzed Suzuki-Miyaura coupling of aryl boronic acids. 3. Ligand employed in the palladium-catalyzed Buchwald-Hartwig aryl amination reaction.

2 mol% L, (C3H5PdCl)2 K3(PO4)3, Toluene, 3 h, 80° MeO Cl +(HO) B MeO Tech. Note (1,2) 2 Ref. (1,2) 90%

2 mol% L, (C3H5PdCl)2 NaOt-Bu, Toluene, MeO Cl + HN MeO N 3 h, 100°C Tech. Note (1,3) Ref. (1)

95% References: 1. US Patent 7129367. 2. Synlett., 2008, 12, 1809.

15-106515-1065 Di-t-butyl(2,2-diphenyl-1-methylvinyl)phosphine, min. 98% Ph Me 250mg (384842‑25‑5) vBRIDP C C 1g C23H31P; FW: 338.47; white to pale yellow xtl. 5g air sensitive, (store cold) Ph P(tBu)2 Note: Sold in collaboration with Takasago. US6455720. Technical Notes: 1. Ligand effective for many classes of palladium-catalyzed coupling of aryl halides, including the Miyaura- Suzuki, Buchwald-Hartwig, Sonogashira, Heck, aryl etherification, and carbonylation reactions. 2. Ligand used in the palladium-catalyzed Suzuki-Miyaura coupling of aryl boronic acids. 3. Ligand employed in the palladium-catalyzed Buchwald-Hartwig aryl amination reaction.

Visit strem.com for new product announcements. 18 PHOSPHORUS (Compounds) 15-1065 Di-t-butyl(2,2-diphenyl-1-methylvinyl)phosphine, min. 98% vBRIDP (384842‑25‑5) (continued)

O H2, (S)-RUCY-XylBINAP (44-0218) OH (C3H5PdCl)2 2 mol% L, Tech. Note (6) R1 R2 2-propanol, 6-21 h R1 R2 MeO Cl + (HO) B MeO Tech. Note (1,2) Ref. (4) 2 K (PO ) , Toluene, Ref. (1,2) R1 = Ph, R2 = Me: >99% ee (R) 3 4 3 3 h, 80° 90%

1) CuCl/L Ph B2Pin2, NaOtBu OH Ph 2 mol% L, (C3H5PdCl)2 THF/MeOH Tech. Note (7) NaOt-Bu, Toluene, MeO Cl + HN MeO N Ph N Ph Ph N Ph Ref. (5) 3 h, 100°C Tech. Note (1,3) 2) reduction H Ref. (1) 3) oxidation References: 1. J. Am. Chem. Soc., 2003, 125, 2507. 95% 2. J. Am. Chem. Soc., 2005, 127, 10164 References: 3. Tetrahedron, 2008, 64, 821. 1. US Patent 7129367. 4. J. Am. Chem. Soc., 2011, 133, 10696. 2. Synlett., 2008, 12, 1809. 5. Org. Lett., 2013, 15, 4810. 15-100715-1007 Dicyclohexyl(2,2-diphenyl-1-methylcyclopropyl) Ph Me 250mg 15-047715-0477 (S)-(-)-2,2’-Bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl, 98% (S)-(-)-XylBINAP 250mg phosphine Cy-cBRIDP (1023330‑38‑2) 1g (135139‑00‑3) 1g C H P; FW: 404.57; white to pale yellow solid 5g 28 37 Ph PCy2 C52H48P2; FW: 734.90; white to pale yellow xtl.; m.p. 203-206° 5g air sensitive, (store cold) Note: Sold in collaboration with Takasago. Takasago BINAP Ligand Kit component. Technical Note: Note: Sold in collaboration with Takasago. US7129367B2. Technical Notes: 1. See 15-0476 (page 17) 1. Ligand effective for many classes of palladium-catalyzed coupling of aryl halides, including the Miyaura- 15-100515-1005 Di-t-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl) Ph Me 250mg Suzuki, Buchwald-Hartwig, Sonogashira, Heck, aryl etherification, and carbonylation reactions. phosphine cBRIDP (742103‑27‑1) 1g 2. Ligand used in the palladium catalyzed Suzuki-Miyaura coupling of aryl boronic acids. C24H33P; FW: 352.49; white to pale yellow solid 5g 3. Ligand employed in the palladium-catalyzed Buchwald-Hartwig aryl amination reaction. air sensitive, (store cold) Ph P(tBu)2 Note: Sold in collaboration with Takasago. US7129367B2. 2 mol% L, (C3H5PdCl)2 Technical Notes: K3(PO4)3, Toluene, 3 h, 80° Tech. Note (1,2) 1. Ligand effective for many classes of palladium-catalyzed coupling of aryl halides, including the Miyaura- MeO Cl + (HO)2B MeO Suzuki, Buchwald-Hartwig, Sonogashira, Heck, aryl etherification, and carbonylation reactions. Ref. (1,2) 2. Ligand used in the palladium catalyzed Suzuki-Miyaura coupling of aryl boronic acids. 90% 3. Ligand employed in the palladium-catalyzed Buchwald-Hartwig aryl amination reaction. 2 mol% L, (C H PdCl) 3 5 2 2 mol% L, (C3H5PdCl)2 K (PO ) , Toluene, 3 h, 80° 3 4 3 Tech. Note (1,2) NaOt-Bu, Toluene, MeO Cl +(HO)2B MeO MeO Cl + HN MeO N Ref. (1,2) 3 h, 100°C Tech. Note (1,3) 90% Ref. (1)

95% 2 mol% L, (C3H5PdCl)2 NaOt-Bu, Toluene, References: MeO Cl + HN MeO N 3 h, 100°C Tech. Note (1,3) 1. US Patent 7129367. 2. Synlett., 2008, 12, 1809. Ref. (1)

15-106215-1062 Dicyclohexyl(2,2-diphenyl-1-methylvinyl)phosphine Ph Me 250mg 95% Cy-vBRIDP (384842‑24‑4) CC 1g C H P; FW: 366.52; white to pale yellow solid 5g References: 25 35 Ph PCy air sensitive, (store cold) 2 1. US Patent 7129367. Note: Sold in collaboration with Takasago. US6455720. 2. Synlett., 2008, 12, 1809. Technical Notes: 15-106515-1065 Di-t-butyl(2,2-diphenyl-1-methylvinyl)phosphine, min. 98% Ph Me 250mg 1. Ligand used in the Pd-catalyzed amination of aryl halides. (384842‑25‑5) vBRIDP C C 1g 2. Ligand used for Suzuki-Miyaura coupling. C23H31P; FW: 338.47; white to pale yellow xtl. 5g R R air sensitive, (store cold) Ph P(tBu)2 Pd(OAc)2 Note: Sold in collaboration with Takasago. US6455720. X + R'2NH NR'2 Tech. Note (1) Technical Notes: Ligand Ref. (1) 1. Ligand effective for many classes of palladium-catalyzed coupling of aryl halides, including the Miyaura- NaOt-Bu, toluene Suzuki, Buchwald-Hartwig, Sonogashira, Heck, aryl etherification, and carbonylation reactions. 2. Ligand used in the palladium-catalyzed Suzuki-Miyaura coupling of aryl boronic acids. 3. Ligand employed in the palladium-catalyzed Buchwald-Hartwig aryl amination reaction.

19 [email protected] . [email protected] . [email protected] . [email protected] PHOSPHORUS (Compounds) 15-1062 (R)-(+)-2-(Diphenylphosphino)-2’-methoxy-1,1’-binaphthyl, 99% (R)-MOP (145964‑33‑6) (continued) R Pd(OAc) , L, KF R R R 2 Tech. Note (2) X (HO)2B Ref. (2) References: 1. Adv. Synth. Catal., 2007, 349, 2089. 2. Synlett, 2007, 20, 3206.

15-177515-1775 (R)-(+)-2-(Diphenylphosphino)-2’-methoxy-1,1’- 100mg binaphthyl, 99% (R)-MOP (145964‑33‑6) 500mg

C33H25OP; FW: 468.53; white pwdr.; m.p. 177-179° air sensitive OMe Note: Sold in collaboration with Takasago. PPh2 Technical Notes: 1. Efficient catalyst for the enantioselective hydrosilyation of 1-alkenes to optically active 2-alcohols. 2. Ligand for palladium-catalyzed asymmetric reduction of allylic esters. 3. Ligand for the rhodium-catalyzed asymmetric arylation of imines with organostannanes. 4. Ligand for the rhodium-catalyzed asymmetric addition of aryl- and alkenylboronic acids to Isatins. 5. Ligand for desymmetrization of malonamides via an enantioselective intramolecular Buchwald-Hartwig reaction.

SiCl3 OH + HSiCl Pd/MOP 1. EtOH/Et3N 3 Tech. Note (1) 2. H2O2 Ref. (1,2) 70%, 94% ee

+ 1 Pd/MOP R1 R OCO2Me Tech. Note (2) HCOOH 2 Ref. (3) R2 R

2 2 SO3Ar SO Ar + HN N 3 Rh/MOP Tech. Note (3) + Ar3–SnMe Ref. (4) 3 Ar1 Ar3 Ar1 H

O HO R R1 R1 Rh/MOP+ O + RB(OH)2 O N N Tech. Note (4) Ref. (5) R2 R2 up to 98% yield up to 93% ee

O O O O R R R R N N Pd(OAc)2/L N N H H H Tech. Note (5) Br Ref. (6)

References: 1. J. Am. Chem. Soc., 1991, 113, 9887. 2. Acc. Chem. Res., 2000, 33, 354. (review) 3. J. Am. Chem. Soc., 1994, 116, 775. 4. J. Am. Chem. Soc., 2000, 122, 976. 5. Angew. Chem. Int. Ed., 2006, 45, 3353. 6. Tetrahedron Lett., 2009, 50, 4170

Visit strem.com for new product announcements. 20 PHOSPHORUS (Compounds)

15-177615-1776 (S)-(-)-2-(Diphenylphosphino)-2’-methoxy-1,1’-binaphthyl, 99% 100mg (S)-MOP (134484‑36‑9) 500mg C H OP; FW: 468.53; white pwdr.; m.p. 175-179° R R Pd(OAc) , L, KF R R 33 25 2 Tech. Note (2) air sensitive X (HO) B 2 Ref. (2) Note: Sold in collaboration with Takasago. Technical Note: References: 1. See 15-1775 (page 20) 1. Adv. Synth. Catal., 2007, 349, 2089. 2. Synlett, 2007, 20, 3206. 96-6950 Takasago BINAP Ligand Kit See page 44 15-177515-1775 (R)-(+)-2-(Diphenylphosphino)-2’-methoxy-1,1’- 100mg binaphthyl, 99% (R)-MOP (145964‑33‑6) 500mg 96-6900 Takasago SEGPHOS® Ligand Kit See page 48 C33H25OP; FW: 468.53; white pwdr.; m.p. 177-179° air sensitive OMe Note: Sold in collaboration with Takasago. PPh2 RHODIUM (Compounds) Technical Notes: 45-018545-0185 (2S,3S)-(+)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene(1,5- 100mg 1. Efficient catalyst for the enantioselective hydrosilyation of 1-alkenes to cyclooctadiene)rhodium(I) tetrafluoroborate, min. 97% (S,S)-NORPHOS-Rh 500mg optically active 2-alcohols. (78355‑59‑6) 2. Ligand for palladium-catalyzed asymmetric reduction of allylic esters. + - [Rh(C8H12)(C31H28P2)] BF4 ; FW: 760.39; red‑orange pwdr. 3. Ligand for the rhodium-catalyzed asymmetric arylation of imines with organostannanes. air sensitive 4. Ligand for the rhodium-catalyzed asymmetric addition of aryl- and alkenylboronic acids to Isatins. Note: Sold in collaboration with Takasago. 5. Ligand for desymmetrization of malonamides via an enantioselective intramolecular Buchwald-Hartwig reaction. RUTHENIUM (Compounds) SiCl OH Pd/MOP 3 1. EtOH/Et N 44-0071 250mg + HSiCl3 3 44-0071 Carbonylchlorohydrido[bis(2-(diphenylphosphinoethyl) H Tech. Note (1) amino]ruthenium(II), min.98% Ru-MACHO® Ph 1g 2. H O H 2 2 Ref. (1,2) (1295649‑40‑9) N P 5g 70%, 94% ee C29H30ClNOP2Ru; FW: 607.03; white to yellow pwdr. Ru Ph air sensitive P CO + Note: Sold in collaboration with Takasago. US Patent 8471048 Ph 1 Pd/MOP R1 Cl R OCO2Me Tech. Note (2) Technical Notes: Ph HCOOH Ref. (3) 1. Highly efficient ruthenium-catalyzed N-formylation of amines with hydrogen and carbon dioxide. 2 R2 R 2. Ruthenium- catalyzed hydrogen generation from glycerol and selective synthesis of lactic acid. 3. See 44-0074. 2 2 SO3Ar SO Ar + HN 1 N 3 Rh/MOP Tech. Note (3) R 3 + Ar –SnMe Ref. (4) 1 2 3 Ar1 Ar3 R R Ar1 H N Ru complex H N CO2 + H2 + 2 + H O C R 2 Tech. Note (1) O HO R 120°C Ref. (1) R1 R1 H R = H or Me Rh/MOP+ O O + RB(OH)2 O N N Tech. Note (4) TONs of up to 1940000 Ref. (5) R2 R2 12 recycles up to 98% yield up to 93% ee OH Ru catalyst HO OH NaOH, H2O C CH O O O O H2 + 3 Tech. Note (2) R R R R OH 110°C, 24 hr O Ref. (2) N N Pd(OAc)2/L N N H H H Tech. Note (5) OH Br Ref. (6) References: 1. Angew. Chem., Int. Ed., 2015, 54, 6186 2. Green Chem., 2015, 17, 193 References: 1. J. Am. Chem. Soc., 1991, 113, 9887. 44-007444-0074 Carbonylhydrido(tetrahydroborato)[bis(2- H 250mg H Ph 2. Acc. Chem. Res., 2000, 33, 354. (review) diphenylphosphinoethyl) amino]ruthenium(II), min.98% 1g (1295649‑41‑0) N P 3. J. Am. Chem. Soc., 1994, 116, 775. Ru-MACHO™-BH 5g C H BNOP Ru; FW: 586.41; white to yellow pwdr. Ru Ph 4. J. Am. Chem. Soc., 2000, 122, 976. 29 34 2 air sensitive 5. Angew. Chem. Int. Ed., 2006, 45, 3353. P CO Note: Sold in collaboration with Takasago. US Patent 8471048. Ph 6. Tetrahedron Lett., 2009, 50, 4170 Ph H Technical Notes: 1. Catalyst used for hydrogenation of esters without addition of base. BH3 2. See 44-0071.

21 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds) 44-0074 Carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl) amino]ruthenium(II), (continued) min.98% Ru-MACHO™-BH (1295649‑41‑0) Ru-cat. (S/C = 500) NHBoc NHBoc H2 (5 MPa) Tech. Note (1) OH CO2Me Ref. (1) THF, 80°C, 16h 100%, 99% ee

OBn Ru-cat. (S/C = 500) H (5 MPa) OBn 2 Tech. Note (1) CO Me OH 2 Ref. (1) THF, 80°C, 16h 98.5% ee 99%, 98.5% ee

Ru-cat. (S/C = 250) NHBoc NHBoc H2 (5 MPa) CO2Me Tech. Note (1) OH Ref. (1) THF, 80°C, 16h 99% ee 95.9%, 99% ee

Ru-cat. (S/C = 250) OTBS OTBS H2 (5 MPa) CO2Me Tech. Note (1) OH Ref. (1) THF, 80°C, 16h 99% ee 87.9%, 99% ee References: 1. US. Pat. 8471048.

44-015644-0156 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl] F 250mg (pentafluorophenylsulfonyl)amido}(p-cymene) F F 1g ruthenium(II), min. 90% RuCl[(R,R)-Fsdpen](p-cymene) 5g (1026995‑71‑0) F F C30H28ClF5N2O2RuS; FW: 712.14; orange to brown pwdr. O O air sensitive S Me Note: Sold in collaboration with Takasago. Ph N Technical Note: Ru 1. Catalyst used in the asymmetric transfer hydrogenation of ketones iPr using formic acid-triethylamine mixture. Ph N Cl H H O OH

1 cat. 1 Tech. Note (1) R R Ref. (1) R2 R2

HCO2H-(C2H5)3N References: 1. J .Am. Chem. Soc., 1996, 118, 2521.

44-015744-0157 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl](pentafluorophenylsulfonyl) 250mg amido}(p-cymene)ruthenium(II), min. 90% RuCl[(S,S)-Fsdpen](p-cymene) 1g (1026995‑72‑1) 5g

C30H28ClF5N2O2RuS; FW: 712.14; orange to brown pwdr. air sensitive Note: Sold in collaboration with Takasago. Takasago ATH Catalyst Kit component.

44-014944-0149 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl](4-toluenesulfonyl)amido} 250mg (p-cymene)ruthenium(II), min. 90% RuCl[(S,S)-Tsdpen](p-cymene) 1g (192139‑90‑5) 5g

C31H35ClN2O2RuS; FW: 636.21; yellow to dark brown solid air sensitive Note: Sold in collaboration with Takasago. Takasago ATH Catalyst Kit component.

Visit strem.com for new product announcements. 22 RUTHENIUM (Compounds)

44-014844-0148 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl](4-tolue- Me 250mg nesulfonyl)amido}(p-cymene)ruthenium(II), min. 95% 1g Ru-cat. (S/C = 500) RuCl[(R,R)-Tsdpen](p-cymene) (192139‑92‑7) 5g NHBoc NHBoc C31H35ClN2O2RuS; FW: 636.21; yellow to dark brown solid H2 (5 MPa) Tech. Note (1) OH air sensitive CO2Me Ref. (1) O O THF, 80°C, 16h Note: Sold in collaboration with Takasago. Takasago ATH S Me 100%, 99% ee Catalyst Kit component. Ph N Technical Note: Ru-cat. (S/C = 500) 1. This catalyst has shown to effect highly enantioselective hydrogenation Ru OBn iPr H (5 MPa) OBn of functionalized ketones where the substituents are dialkylamino, Cl 2 Tech. Note (1) Ph N CO Me OH hydoxy, siloxy, carbonyl, ester, amide or thioester. 2 Ref. (1) H H THF, 80°C, 16h 98.5% ee 99%, 98.5% ee n Cat. n CO Et CO2Et 2 HCO2H, Et3N Tech. Note (1) NHBoc Ru-cat. (S/C = 250) H (5 MPa) NHBoc O OH Ref. (1) CO Me 2 Tech. Note (1) 2 ee up to 99% OH Ref. (1) THF, 80°C, 16h syn:anti up to >99:1 99% ee 95.9%, 99% ee X Cat. HCO2H, Et3N X Ru-cat. (S/C = 250) n n OTBS OTBS H2 (5 MPa) DPPA/DBU; LiAlH4 or PPh3/H2O Tech. Note (1) CO2Me Tech. Note (1) R' R R' R OH Ref. (1) Ref. (2) THF, 80°C, 16h O NH2 99% ee 87.9%, 99% ee n = 0,1; R = alkyl, F, OAc; X = CH2, O References: 1. US. Pat. 8471048. O OH

44-015644-0156 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl] F 250mg MeO NMe MeO NMe2 2 Cat. HCO2H, Et3N Tech. Note (1) (pentafluorophenylsulfonyl)amido}(p-cymene) F F 1g ruthenium(II), min. 90% RuCl[(R,R)-Fsdpen](p-cymene) 5g EtOAc, rt, 7 days Ref. (3) MeO MeO (1026995‑71‑0) 98% ee F F C30H28ClF5N2O2RuS; FW: 712.14; orange to brown pwdr. O O air sensitive S Me Me Me Note: Sold in collaboration with Takasago. Ph N Technical Note: O Ru N O N 1. Catalyst used in the asymmetric transfer hydrogenation of ketones iPr 0.2 mol% Cat. Tech. Note (1) Ph N Cl using formic acid-triethylamine mixture. Me HCO H, DIPEA Me Ref. (4-6) H H O 2 HO Me Me O OH 95% ee

Cat. HCO H, Et N 1 cat. 1 Tech. Note (1) 2 3 R R Ref. (1) R2 R2 N NH Tech. Note (1) Ref. (7,8) HCO H-(C H ) N 2 2 5 3 R' R' References: References: 1. J .Am. Chem. Soc., 1996, 118, 2521. 1. Tetrahedron, 2007, 63, 7532

2. Tetrahedron, 2007, 63, 6755 44-015744-0157 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl](pentafluorophenylsulfonyl) 250mg 3. Tetrahedron: Asymmetry, 2009, 20, 1138 amido}(p-cymene)ruthenium(II), min. 90% RuCl[(S,S)-Fsdpen](p-cymene) 1g 4. J. Org. Chem., , 74, 1411 (1026995‑72‑1) 5g 2009 5. Org. Lett., , 9, 2461 C H ClF N O RuS; FW: 712.14; orange to brown pwdr. 2007 30 28 5 2 2 6. Org. Lett., , 11, 935 air sensitive 2009 7. Angew. Chem. Int. Ed., , 48, 7616 Note: Sold in collaboration with Takasago. Takasago ATH Catalyst Kit component. 2009 8. Bioorg. Med. Chem. Lett., 2008, 18, 4110

44-014944-0149 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl](4-toluenesulfonyl)amido} 250mg (p-cymene)ruthenium(II), min. 90% RuCl[(S,S)-Tsdpen](p-cymene) 1g (192139‑90‑5) 5g

C31H35ClN2O2RuS; FW: 636.21; yellow to dark brown solid air sensitive Note: Sold in collaboration with Takasago. Takasago ATH Catalyst Kit component.

23 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds)

44-015444-0154 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl](4-tolue- Me 250mg nesulfonyl)amido}(mesitylene)ruthenium(II), min. 90% 1g RuCl[(R,R)-Tsdpen(mesitylene) (174813‑82‑2) 5g

C30H33ClN2O2RuS; FW: 622.18; orange pwdr. air sensitive O O Note: Sold in collaboration with Takasago. Takasago ATH S Me Catalyst Kit component. Ph N Me Technical Note: Ru Me 1. Catalyst used in the asymmetric transfer hydrogenation of ketones Ph N Cl using formic acid-triethylamine mixture. H H O OH

1 cat. 1 Tech. Note (1) R R Ref. (1) R2 R2

HCO2H-(C2H5)3N References: 1. J .Am. Chem. Soc., 1996, 118, 2521.

44-015544-0155 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl](4-tolue- Me 250mg nesulfonyl)amido}(mesitylene)ruthenium(II), min. 90% 1g RuCl[(S,S)-Tsdpen](mesitylene) (174813‑81‑1) 5g

C30H33ClN2O2RuS; FW: 622.18; yellow to dark brown solid air sensitive O O Note: Sold in collaboration with Takasago. US7129367B2. S Me Takasago ATH Catalyst Kit component. Ph N Me Technical Note: Ru Me 1. See 44-0154 (page 24) Ph N Cl H H

44-010244-0102 Chloro{(R)-(-)-5,5’-bis[di(3,5-di-t-butyl-4- MeO 250mg tBu methoxyphenyl)phosphino]-4,4’-bi-1,3- 1g tBu tBu benzodioxole}(p-cymene)ruthenium(II) 5g O OMe chloride [RuCl(p-cymene)((R)-dtbm- Me segphos®)]Cl (944451‑32‑5) P tBu O [C H ClO P Ru]+Cl-; FW: 1485.72; + 84 114 8 2 Cl- yellow to dark brown pwdr.; m.p. >100° dec. Ru O Cl air sensitive P tBu iPr Note: Sold in collaboration with Takasago. O Takasago SEGPHOS® Ru Catalyst Kit OMe tBu component. tBu tBu Technical Note: MeO 1. See 15-0066.

44-010344-0103 Chloro{(S)-(+)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4’- 250mg bi-1,3-benzodioxole}(p-cymene)ruthenium(II) chloride [RuCl(p-cymene) 1g ((S)-dtbm-segphos®)]Cl (944451‑33‑6) 5g + - [C84H114ClO8P2Ru] Cl ; FW: 1485.72; orange to brown pwdr.; m.p. >100° dec. air sensitive Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit component. Technical Note: 1. See 44-0102 (page 24)

Visit strem.com for new product announcements. 24 RUTHENIUM (Compounds)

44-015444-0154 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl](4-tolue- Me 250mg 44-009644-0096 Chloro[(R)-(+)-5,5’-bis(diphenylphosphino)- O 250mg nesulfonyl)amido}(mesitylene)ruthenium(II), min. 90% 1g 4,4’-bi-1,3-benzodioxole](p-cymene) Me 1g Ph RuCl[(R,R)-Tsdpen(mesitylene) (174813‑82‑2) 5g ruthenium(II) chloride [RuCl(p-cymene) Ph 5g O P C H ClN O RuS; FW: 622.18; orange pwdr. ((R)-segphos®)]Cl (944451‑28‑9) + - 30 33 2 2 Ru Cl + - air sensitive [C48H42ClO4P2Ru] Cl ; FW: 916.77; P Cl O O Me O Ph iPr Note: Sold in collaboration with Takasago. Takasago ATH S yellow pwdr.; m.p. >100° dec. Ph Catalyst Kit component. Ph N air sensitive Me Note: Sold in collaboration with Takasago. O Technical Note: Ru Me Takasago SEGPHOS® Ru Catalyst Kit 1. Catalyst used in the asymmetric transfer hydrogenation of ketones Ph N Cl using formic acid-triethylamine mixture. component. H H Technical Notes: O OH 1. Highly active highly enantioselective catalyst for hydrogenation of functionalized ketones. Slightly higher temperature is necessary to activate the cymene complexes. See 15-0136 . 2. Asymmetric hydrogenation of α-substituted-β-alkyl-β-ketoesters accompanied by dynamic kinetic resolution. cat. Tech. Note (1) R1 R1 Ref. (1) O O OH O R2 R2 HCO H-(C H ) N 2 2 5 3 0.1% cat., CH Cl OEt 2 2 OEt Tech. Note (1) References: + H2 20 Atm, 60° C 91 hr Ref. (1) 1. J .Am. Chem. Soc., 1996, 118, 2521.

44-015544-0155 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl](4-tolue- Me 250mg 98%, 98% ee, 88% de nesulfonyl)amido}(mesitylene)ruthenium(II), min. 90% 1g RuCl[(S,S)-Tsdpen](mesitylene) (174813‑81‑1) 5g References: 1. U.S. Pat. 7038087. C30H33ClN2O2RuS; FW: 622.18; yellow to dark brown solid air sensitive 44-009744-0097 Chloro[(S)-(-)-5,5’-bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole] 250mg O O Me Note: Sold in collaboration with Takasago. US7129367B2. S (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-segphos®)]Cl 1g Takasago ATH Catalyst Kit component. (944451‑29‑0) 5g Ph N Me [C H ClO P Ru]+Cl-; FW: 916.77; ocher to dark brown pwdr.; Ru Me 48 42 4 2 Technical Note: m.p. >100° dec. 1. See 44-0154 (page 24) Ph N Cl air sensitive H H Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru

44-010244-0102 Chloro{(R)-(-)-5,5’-bis[di(3,5-di-t-butyl-4- MeO 250mg Catalyst Kit component. tBu methoxyphenyl)phosphino]-4,4’-bi-1,3- 1g Technical Note: tBu tBu benzodioxole}(p-cymene)ruthenium(II) 5g 1. See 44-0096 (page 25) O OMe chloride [RuCl(p-cymene)((R)-dtbm- Me 44-008444-0084 Chloro[(R)-(+)-2,2’-bis(diphenylphosphino)-1,1’ 250mg Me segphos®)]Cl (944451‑32‑5) P tBu -binaphthyl](p-cymene)ruthenium(II) chloride 1g + - O Ph [C84H114ClO8P2Ru] Cl ; FW: 1485.72; + [RuCl(p-cymene)((R)-binap)]Cl (145926‑28‑9) Ph 5g Ru Cl- P + yellow to dark brown pwdr.; m.p. >100° dec. + - - O Cl [C54H46ClP2Ru] Cl ; FW: 928.87; orange pwdr.; Ru Cl air sensitive P tBu iPr P Cl m.p. >100° dec. Ph iPr Note: Sold in collaboration with Takasago. air sensitive Ph O Takasago SEGPHOS® Ru Catalyst Kit OMe Note: Sold in collaboration with Takasago. tBu component. tBu tBu Takasago BINAP Ru Cymene Catalyst Kit Technical Note: MeO component. 1. See 15-0066. Technical Note:

1. An efficient catalytic asymmetric hydrogenation of diketene. 44-010344-0103 Chloro{(S)-(+)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4’- 250mg bi-1,3-benzodioxole}(p-cymene)ruthenium(II) chloride [RuCl(p-cymene) 1g Ru-Cat., H2, NEt3 O ((S)-dtbm-segphos®)]Cl (944451‑33‑6) 5g O [C H ClO P Ru]+Cl-; FW: 1485.72; orange to brown pwdr.; m.p. >100° dec. Tech. Note (1) 84 114 8 2 O THF O air sensitive Ref. (1) 97% selectivity Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit 92% ee component. Technical Note: References: 1. See 44-0102 (page 24) 1. J. Chem. Soc., Chem. Chem. Commun. 1992, 1725.

25 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds)

44-008644-0086 Chloro[(S)-(-)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] 250mg (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-binap)]Cl 1g (130004‑33‑0) 5g + - [C54H46ClP2Ru] Cl ; FW: 928.87; orange pwdr.; m.p. >100° dec. air sensitive Note: Sold in collaboration with Takasago. Takasago BINAP Ru Cymene Catalyst Kit component. Technical Notes: 1. See 15-0151. 2. This catalyst has shown to effect the highly enantioselective hydrogenation of functionalized ketones where the substituents are dialkylamino, hydoxy, siloxy, carbonyl, ester, amide or thioester. O O O O OH O Cat. Tech. Note (2) Ref. (1) MeO NHt-Bu MeO NHt-Bu

O O OH O Cat. Tech. Note (2) Me Me Ref. (2) Me O Me O References: 1. Tetrahedron Lett., 2008, 49, 4836 2. Appl. Catal. A., 2009, 366, 160

44-009444-0094 Chloro[(R)-(+)-2,2’-bis(diphenylphosphino)- 50mg Me 250mg 5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl] Ph (p-cymene)ruthenium(II) chloride [RuCl(p- Ph P + - cymene)((R)-H8-binap)]Cl (944451‑26‑7) Ru Cl [C H ClP Ru]+Cl-; FW: 936.93; pale yellow pwdr.; P Cl 54 54 2 Ph iPr m.p. >100° dec. Ph air sensitive Note: Sold in collaboration with Takasago. Technical Notes:

1. Biaryl bisphosphine ligand. The H8-BINAP ligand, as the ruthenium complex, catalyzes hydrogenation of unsaturated carboxylic acids to a higher ee than does BINAP. (Ref. 1,2) 2. The ruthenium catalyzed hydrogenation of aryl propenoic acid to produce the drug Ibuprofen.

0.5 mol% [(S)-L]Ru(OAc)2 100 atm H2, MeOH, Tech. Note (1,2) 8 h, rt Ref. (1,2)

COOH COOH 97%, 97%ee References: 1. J. Org. Chem., 1996, 61, 5510 2. Topics Organometal. Chem. 2004, 6, 63, review

44-009544-0095 Chloro[(S)-(-)-2,2’-bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’- 50mg octahydro-1,1’-binaphthyl](p-cymene)ruthenium(II) chloride 250mg

[RuCl(p-cymene)((S)-H8-binap)]Cl (944451‑27‑8) + - [C54H54ClP2Ru] Cl ; FW: 936.93; pale yellow pwdr.; m.p. >100° dec. air sensitive Note: Sold in collaboration with Takasago. Technical Note: 1. See 44-0094 (page 26)

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44-008644-0086 Chloro[(S)-(-)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] 250mg 44-008844-0088 Chloro[(R)-(+)-2,2’-bis(di-p-tolylphosphino)- Me 250mg (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-binap)]Cl 1g 1,1’-binaphthyl](p-cymene)ruthenium(II) 1g (130004‑33‑0) 5g chloride [RuCl(p-cymene)((R)-tolbinap)]Cl Me 5g + - Me [C54H46ClP2Ru] Cl ; FW: 928.87; orange pwdr.; m.p. >100° dec. (131614‑43‑2) + - P air sensitive [C58H54ClP2Ru] Cl ; FW: 984.97; brown pwdr.; + - Note: Sold in collaboration with Takasago. Takasago BINAP Ru Cymene m.p. >100° dec. Ru Cl P Cl Catalyst Kit component. air sensitive Me iPr Technical Notes: Note: Sold in collaboration with Takasago. 1. See 15-0151. Takasago BINAP Ru Cymene Catalyst Kit 2. This catalyst has shown to effect the highly enantioselective hydrogenation of functionalized ketones where component. Me the substituents are dialkylamino, hydoxy, siloxy, carbonyl, ester, amide or thioester. Technical Note: O O O O OH O 1. See 15-0152 (page 12) Cat. Tech. Note (2) Ref. (1) 44-008944-0089 Chloro[(S)-(-)-2,2’-bis(di-p-tolylphosphino)-1,1’-binaphthyl](p-cymene) 250mg MeO NHt-Bu MeO NHt-Bu ruthenium(II) chloride [RuCl(p-cymene)((S)-tolbinap)]Cl (228120‑95‑4) 1g + - [C58H54ClP2Ru] Cl ; FW: 984.97; yellow to dark brown solid; m.p. >100° dec. 5g O O OH O air sensitive Cat. Tech. Note (2) Note: Sold in collaboration with Takasago. Takasago BINAP Ru Cymene Me Me Ref. (2) Me O Me O Catalyst Kit component. References: Technical Note: 1. See 15-0153 (page 13) 1. Tetrahedron Lett., 2008, 49, 4836

2. Appl. Catal. A., 2009, 366, 160 44-0098 44-0098 Chloro{(R)-(+)-5,5’-bis[di(3,5-xylyl) Me Me 250mg Me 44-009444-0094 Chloro[(R)-(+)-2,2’-bis(diphenylphosphino)- 50mg phosphino]-4,4’-bi-1,3-benzodioxole} O 1g 5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl] Me 250mg (p-cymene)ruthenium(II) chloride Me 5g Ph P (p-cymene)ruthenium(II) chloride [RuCl(p- Ph [RuCl(p-cymene)((R)-dm-segphos®)]Cl O Me P + + - (944451‑30‑3) Cl- cymene)((R)-H8-binap)]Cl (944451‑26‑7) Ru Cl Ru + - Cl [C H ClP Ru]+Cl-; FW: 936.93; pale yellow pwdr.; P Cl [C56H58ClO4P2Ru] Cl ; FW: 1028.98; O Me 54 54 2 Ph iPr P iPr m.p. >100° dec. Ph orange to brown pwdr.; m.p. >100° dec. air sensitive O air sensitive Me Note: Sold in collaboration with Takasago. Note: Sold in collaboration with Takasago. Me Me Technical Notes: Takasago SEGPHOS® Ru Catalyst Kit

1. Biaryl bisphosphine ligand. The H8-BINAP ligand, as the ruthenium complex, catalyzes hydrogenation of component. unsaturated carboxylic acids to a higher ee than does BINAP. (Ref. 1,2) Technical Note: 2. The ruthenium catalyzed hydrogenation of aryl propenoic acid to produce the drug Ibuprofen. 1. Ruthenium catalyst used for the asymmetric hydrogenation of β-ketoimides. O O OH O 0.5 mol% BnO C C BnO C Tech. Note (1) [(S)-L]Ru(OAc)2 Ru catalyst Ref. (1) 100 atm H2, MeOH, Tech. Note (1,2) NBn NBn 8 h, rt Ref. (1,2)

COOH COOH References: 1. J. Org. Chem., 2012, 77, 4732 97%, 97%ee References: 44-009944-0099 Chloro{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3-benzodioxole} 250mg 1. J. Org. Chem., 1996, 61, 5510 (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-dm-segphos®)]Cl 1g 2. Topics Organometal. Chem. 2004, 6, 63, review (944451‑31‑4) 5g + - [C56H58ClO4P2Ru] Cl ; FW: 1028.98; orange to brown pwdr.; m.p. >100° dec. 44-009544-0095 Chloro[(S)-(-)-2,2’-bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’- 50mg air sensitive octahydro-1,1’-binaphthyl](p-cymene)ruthenium(II) chloride 250mg Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst [RuCl(p-cymene)((S)-H8-binap)]Cl (944451‑27‑8) Kit component. + - [C54H54ClP2Ru] Cl ; FW: 936.93; pale yellow pwdr.; m.p. >100° dec. Technical Note: air sensitive 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM-SEGPHOS ligand, as the ruthenium Note: Sold in collaboration with Takasago. complex, gives superior enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of Technical Note: α-substituted-β-ketoesters. See 15-0066. 1. See 44-0094 (page 26)

27 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds)

44-009244-0092 Chloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphi- Me Me 250mg no]-1,1’-binaphthyl}(p-cymene)ruthenium(II) Me 1g chloride [RuCl(p-cymene)((R)-xylbinap}]Cl Me 5g P (944451‑24‑5) Me + - + - [C62H62ClP2Ru] Cl ; FW: 1041.08; Ru Cl orange to brown pwdr.; m.p. >100° dec. Me Cl air sensitive P iPr Note: Sold in collaboration with Takasago. Me Takasago BINAP Ru Cymene Catalyst Kit Me Me component. Technical Note: 1. See 15-0150.

44-021744-0217 Chloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl} 100mg [(2R)-(-)-1-(4-methoxyphenyl)- 1’-(4-methoxyphenyl-kC)-3- meth- 250mg yl-1,2-butanediamine]ruthenium(II) (R)-RUCY®XylBINAP 1g (1384974‑38‑2) Me Me 5g Me C71H73ClN2O2P2Ru; FW: 1184.82; yellow to dark brown/green solid P H H Me Cl air sensitive N OMe Note: Sold in collaboration with Takasago. Ru H H Me N H US Patent 9079931. Takasago BINAP Ru P iPr Diamine Catalyst Kit component. Takasago ATH Catalyst Kit component. Me Technical Note: Me Me MeO 1. See 44-0218 (page 28)

44-021844-0218 Chloro{(S)-(-)-2,2’-bis[di(3,5-xylyl) phosphino]-1,1’-binaphthyl}[(2S)- 250mg (+)-1-(4-methoxyphenyl)-1’-(4-methoxyphenyl-kC)-3-methyl-1,2- 1g butanediamine]ruthenium(II) (S)-RUCY®XylBINAP (1312713‑89‑5) 5g C71H73ClN2O2P2Ru; FW: 1184.82; Me Me yellow to dark brown/green solid Me air sensitive P H H Note: Sold in collaboration with Takasago. Me Cl US Patent 9079931. Takasago BINAP Ru N OMe Ru H H Diamine Catalyst Kit component. Takasago Me H P N ATH Catalyst Kit component. iPr Technical Note: Me 1. Catalyst used for the rapid, and highly selective Me Me MeO hydrogenation of ketones.

O OH Ru cat. H2, t-BuOK Tech. Note (1) H2 50 atm, 0.001mol%, 6 min Ref. (1) H2 7 atm, 0.001mol%, 15 min >99% yield >99% ee

"trans-RuCl2(xylbinap)(daipen) 0.001 mol%, 240 min"

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44-009244-0092 Chloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphi- Me Me 250mg 44-0218 Chloro{(S)-(-)-2,2’-bis[di(3,5-xylyl) phosphino]-1,1’-binaphthyl}[(2S)- (+)-1-(4-methoxy no]-1,1’-binaphthyl}(p-cymene)ruthenium(II) Me 1g (continued) phenyl)-1’-(4-methoxyphenyl-kC)-3-methyl-1,2-butanediamine]ruthenium(II) chloride [RuCl(p-cymene)((R)-xylbinap}]Cl Me 5g (S)-RUCY®XylBINAP (1312713‑89‑5) (944451‑24‑5) P Me OH + - + - O [C62H62ClP2Ru] Cl ; FW: 1041.08; Ru Cl orange to brown pwdr.; m.p. >100° dec. Me Cl Ru cat. (0.05mol%) OH OH air sensitive P iPr H2 (10 atm), DBU Note: Sold in collaboration with Takasago. Tech. Note (1) Me Takasago BINAP Ru Cymene Catalyst Kit Me Me Ref. (1) component. Technical Note: >99% yield 1. See 15-0150. >95% ee

44-009344-0093 Chloro{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}(p-cymene) 250mg ruthenium(II) chloride [RuCl(p-cymene)((S)-xylbinap)]Cl (944451‑25‑6) 1g O OH + - [C62H62ClP2Ru] Cl ; FW: 1041.08; orange to brown pwdr.; m.p. >100° dec. 5g air sensitive Ru cat. (0.05mol%) Note: Sold in collaboration with Takasago. Takasago BINAP Ru Cymene H2 (10 atm), t-BuOK * Tech. Note (1) Catalyst Kit component. Technical Note: Ref. (1) 1. See 44-0092 (page 28) "trans-RuCl (xylbinap)(daipen) 0.1mole%, 2 42% yield, 90% ee" >99% yield 44-021744-0217 Chloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl} 100mg 97% ee [(2R)-(-)-1-(4-methoxyphenyl)- 1’-(4-methoxyphenyl-kC)-3- meth- 250mg yl-1,2-butanediamine]ruthenium(II) (R)-RUCY®XylBINAP 1g (1384974‑38‑2) Me Me 5g O Ru cat. (0.002mol%) OH Me H2 (10 atm), t-BuOK C71H73ClN2O2P2Ru; FW: 1184.82; * yellow to dark brown/green solid P H H Tech. Note (1) Me Cl air sensitive N OMe N "trans-RuCl (xylbinap)(daipen) 0.005mole%, N Ref. (1) Note: Sold in collaboration with Takasago. Ru H H 2 Me N H 50% yield, 86% ee" US Patent 9079931. Takasago BINAP Ru P >99% yield iPr Diamine Catalyst Kit component. Takasago 95% ee ATH Catalyst Kit component. Me References: Technical Note: Me Me MeO 1. (a) US. Pat. 9079931. (b) J.Am.Chem. Soc., 2011, 133, 10696. 1. See 44-0218 (page 28) 44-025544-0255 Chloro{N-[(1R,2R)-2-[(S)-[2-[[1,2,3,4,5,6-η)-4- 250mg Me 44-021844-0218 Chloro{(S)-(-)-2,2’-bis[di(3,5-xylyl) phosphino]-1,1’-binaphthyl}[(2S)- 250mg methylphenyl]methoxy]ethyl]amino]-1,2-diphenylet O 1g O (+)-1-(4-methoxyphenyl)-1’-(4-methoxyphenyl-kC)-3-methyl-1,2- 1g hylmethanesulfonamidato}ruthenium(II) Me S Ru 5g butanediamine]ruthenium(II) (S)-RUCY®XylBINAP (1312713‑89‑5) 5g (R,R)-Ms-DENEB® (1333981‑86‑4) N Cl O C H ClN O P Ru; FW: 1184.82; C25H29ClN2O3RuS; FW: 574.10; light to dark brown pwdr. N 71 73 2 2 2 Me Me H yellow to dark brown/green solid Me Note: Sold in collaboration with Takasago. US. Patent Ph air sensitive 9217005. Takasago ATH Catalyst Kit component. Technical Notes: Ph Note: Sold in collaboration with Takasago. P H H Me Cl 1. Catalyst used for both hydrogenation and asymmetric transfer hydrogenation. US Patent 9079931. Takasago BINAP Ru N OMe Ru H H 2. Ruthenium catalyst used as a key intermediate in a synthesis of a receptor agonist. Diamine Catalyst Kit component. Takasago Me H P N ATH Catalyst Kit component. iPr O OH Technical Note: Ru DENEB complex Me 1. Catalyst used for the rapid, and highly selective Me Me MeO C Tech. Note (1) hydrogenation of ketones. Ar R HCO2H + NEt3 Ar R Ref. (1) or OH O Hydrogenation S/C = 200-30,000 Up to >99% ee Ru cat. H2, t-BuOK O O HO TBSO Tech. Note (1) C Br C NHCbz NHCbz NH2 . 2AcOH H2 50 atm, 0.001mol%, 6 min Ref. (1) HCO H / NEt H2 7 atm, 0.001mol%, 15 min 2 3 >99% yield Ru(S.S)-Ms-DENEB Tech. Note (2) >99% ee C C C C N O N O N O N O Ref. (2) "trans-RuCl (xylbinap)(daipen) 0.001 mol%, 240 min" H H H H 2 OBn OBn OBn OH 99% ee >99% ee

References: 1. J. Am. Chem. Soc., 2011, 133, 14960 2. Org. Process Res. Dev., 2015, 19, 315

29 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds)

44-025644-0256 Chloro{N-[(1S,2S)-2-[(R)-[2-[[1,2,3,4,5,6-η)-4-methylphenyl]methoxy]ethyl] 250mg amino]-1,2-diphenylethylmethanesulfonamidato}ruthenium(II) 1g (S,S)-Ms-DENEB® (1361318‑83‑3) 5g

C25H29ClN2O3RuS; FW: 574.10; light to dark brown pwdr. Note: Sold in collaboration with Takasago. US. Patent 9217005. Takasago ATH Catalyst Kit component.

44-018044-0180 Diacetato{(R)-(-)-5,5’-bis[di(3,5-di-t-butyl- OMe 250mg 4-methoxyphenyl)phosphino]-4,4’-bi-1,3- tBu tBu 1g tBu benzodioxole}ruthenium(II) Ru(OAc)2[(R)- 5g OMe dtbm-segphos®] (1025477‑38‑6) O Me C H O P Ru; FW: 1398.69; 78 106 12 2 tBu O yellow to brownish‑red to dark green solid O P O air sensitive Ru O Note: Sold in collaboration with Takasago. O P tBu O Takasago SEGPHOS® Ru Catalyst Kit component. O OMe Me tBu tBu tBu OMe Technical Note: 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM-SEGPHOS ligand, as the ruthenium complex, gives superior enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of α-substituted-β-ketoesters. See 15-0066.

44-018144-0181 Diacetato{(S)-(+)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphi- 250mg

no]-4,4’-bi-1,3-benzodioxole}ruthenium(II) Ru(OAc)2[(S)-dtbm-seg- 1g phos®] (1025476‑84‑9) 5g

C78H106O12P2Ru; FW: 1398.69; yellow to brownish‑red to dark green solid air sensitive Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit component.

44-016844-0168 Diacetato[(R)-(+)-5,5’-bis(diphenylphosphino)- O 250mg Me 4,4’-bi-1,3-benzodioxole]ruthenium(II) Ph 1g Ph O Ru(OAc)2[(R)-segphos®] (944450‑48‑0) O 5g P O C42H34O8P2Ru; FW: 829.73; dark yellow pwdr.; Ru m.p. >100° dec. P O O Ph O air sensitive Ph Note: Sold in collaboration with Takasago. O Me Takasago SEGPHOS® Ru Catalyst Kit component. Technical Notes: 1. Highly active highly enantioselective catalyst for hydrogenation of functionalized ketones. The acetate salts are frequently used for hydrogenation of allyl alcohols, unsaturated carboxylic acids and reductive amination. See 15-0136. 2. Asymmetric hydrogenation of substituted allyl alcohols.

Tech. Note (1) Ref. (1) OH + H2 OH

References: 1. U.S. Pat. 6342644.

44-016944-0169 Diacetato[(S)-(-)-5,5’-bis(diphenylphosphino)-4,4’-bi-1,3- 250mg

benzodioxole]ruthenium(II) Ru(OAc)2[(S)-segphos®] (373650‑12‑5) 1g

C42H34O8P2Ru; FW: 829.73; yellow to black solid; m.p. >100° dec. 5g air sensitive Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit component. Technical Note: 1. See 44-0168 (page 30)

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44-0256 250mg 44-0152 250mg 44-0256 Chloro{N-[(1S,2S)-2-[(R)-[2-[[1,2,3,4,5,6-η)-4-methylphenyl]methoxy]ethyl] 44-0152 Diacetato[(R)-(+)-2,2’-bis(diphenylphosphino)- Me amino]-1,2-diphenylethylmethanesulfonamidato}ruthenium(II) 1g 1,1’-binaphthyl]ruthenium(II) Ru(OAc)2[(R)-binap] Ph 1g (S,S)-Ms-DENEB® (1361318‑83‑3) 5g (325146‑81‑4) Ph O 5g P O C H ClN O RuS; FW: 574.10; light to dark brown pwdr. C H O P Ru; FW: 841.83; ocher to green pwdr. ; Ru 25 29 2 3 48 38 4 2 P O Ph Note: Sold in collaboration with Takasago. US. Patent 9217005. m.p. >100° dec. Ph O Takasago ATH Catalyst Kit component. air sensitive Me Note: Sold in collaboration with Takasago. 44-018044-0180 Diacetato{(R)-(-)-5,5’-bis[di(3,5-di-t-butyl- OMe 250mg 4-methoxyphenyl)phosphino]-4,4’-bi-1,3- tBu tBu 1g US. Patent 7626034. Takasago BINAP Ru Acetate benzodioxole}ruthenium(II) Ru(OAc) [(R)- tBu 5g Catalyst Kit component. 2 Technical Note: dtbm-segphos®] (1025477‑38‑6) OMe Me O 1. Catalyst system that exhibits very high catalytic activity and enantioselectivity in the hydrogenation of a wide C H O P Ru; FW: 1398.69; 78 106 12 2 tBu O range of substrates. yellow to brownish‑red to dark green solid O P O air sensitive Ru O 44-015344-0153 Diacetato[(S)-(-)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] 250mg Note: Sold in collaboration with Takasago. O P ruthenium(II) Ru(OAc) [(S)-binap] (261948‑85‑0) 1g tBu O 2 Takasago SEGPHOS® Ru Catalyst Kit C48H38O4P2Ru; FW: 841.83; pale yellow pwdr.; m.p. >100° dec. 5g component. O OMe Me air sensitive tBu Note: Sold in collaboration with Takasago. Takasago BINAP Ru Acetate tBu tBu Catalyst Kit component. OMe Technical Note: Technical Note: 1. See 44-0152 (page 31) 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM-SEGPHOS ligand, as the ruthenium 44-016644-0166 Diacetato[(R)-(+)-2,2’-bis(diphenylphosphino)- 50mg complex, gives superior enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of Me 250mg α-substituted-β-ketoesters. See 15-0066. 5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl] Ph (374067‑51‑3) Ph O ruthenium(II) Ru(OAc)2[(R)-H8-binap] P 44-018144-0181 Diacetato{(S)-(+)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphi- 250mg C H O P Ru; FW: 849.89; ocher to olive solid; O 48 46 4 2 Ru O no]-4,4’-bi-1,3-benzodioxole}ruthenium(II) Ru(OAc) [(S)-dtbm-seg- 1g P 2 m.p. >100° dec. Ph O phos®] (1025476‑84‑9) 5g air sensitive Ph Me C78H106O12P2Ru; FW: 1398.69; yellow to brownish‑red to dark green solid Note: Sold in collaboration with Takasago. air sensitive Technical Notes: Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru 1. Biaryl bisphosphine ligand. The H8-BINAP ligand, as the ruthenium complex, catalyzes hydrogenation of Catalyst Kit component. unsaturated carboxylic acids to a higher ee than does BINAP. (Ref. 1,2)

44-016844-0168 Diacetato[(R)-(+)-5,5’-bis(diphenylphosphino)- O 250mg 2. The ruthenium catalyzed hydrogenation of aryl propenoic acid to produce the drug Ibuprofen. Me 4,4’-bi-1,3-benzodioxole]ruthenium(II) Ph 1g Ph O Ru(OAc)2[(R)-segphos®] (944450‑48‑0) O 5g P O 0.5 mol% C42H34O8P2Ru; FW: 829.73; dark yellow pwdr.; Ru m.p. >100° dec. P O [(S)-L]Ru(OAc)2 O Ph O air sensitive Ph 100 atm H2, MeOH, Tech. Note (1,2) Note: Sold in collaboration with Takasago. O Me 8 h, rt Ref. (1,2) Takasago SEGPHOS® Ru Catalyst Kit component. Technical Notes: COOH COOH 1. Highly active highly enantioselective catalyst for hydrogenation of functionalized ketones. The acetate salts 97%, 97%ee are frequently used for hydrogenation of allyl alcohols, unsaturated carboxylic acids and reductive amination. References: See 15-0136. 1. J. Org. Chem., 1996, 61, 5510 2. Asymmetric hydrogenation of substituted allyl alcohols. 2. Topics Organometal. Chem. 2004, 6, 63, review

44-016744-0167 Diacetato[(S)-(-)-2,2’-bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’-octahydro- 50mg

1,1’-binaphthyl]ruthenium(II) Ru(OAc)2[(S)-H8-binap] (142962‑95‑6) 250mg Tech. Note (1) C48H46O4P2Ru; FW: 849.89; yellow to dark brown solid; m.p. >100° dec. air sensitive OH + H2 Ref. (1) OH Note: Sold in collaboration with Takasago. Technical Note: 1. See 44-0166 (page 31) References:

1. U.S. Pat. 6342644. 44-016244-0162 Diacetato[(R)-(+)-2,2’-bis(di-p-tolylphosphino)- Me 250mg

1,1’-binaphthyl]ruthenium(II) Ru(OAc)2[(R)- 1g 44-016944-0169 Diacetato[(S)-(-)-5,5’-bis(diphenylphosphino)-4,4’-bi-1,3- 250mg Me tolbinap] (116128‑29‑1) Me 5g benzodioxole]ruthenium(II) Ru(OAc) [(S)-segphos®] (373650‑12‑5) 1g 2 C H O P Ru; FW: 897.94; brown pwdr.; O C H O P Ru; FW: 829.73; yellow to black solid; m.p. >100° dec. 5g 52 46 4 2 P 42 34 8 2 m.p. >100° dec. O air sensitive Ru air sensitive P O Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Note: Sold in collaboration with Takasago. O Catalyst Kit component. Me Technical Note: Takasago BINAP Ru Acetate Catalyst Kit Me 1. See 44-0168 (page 30) component. Me

31 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds)

44-016344-0163 Diacetato[(S)-(-)-2,2’-bis(di-p-tolylphosphino)-1,1’-binaphthyl] 250mg

ruthenium(II) Ru(OAc)2[(S)-tolbinap] (106681‑15‑6) 1g

C52H46O4P2Ru; FW: 897.94; brown pwdr.; m.p. >100° dec. 5g air sensitive Note: Sold in collaboration with Takasago. Takasago BINAP Ru Acetate Catalyst Kit component.

44-017444-0174 Diacetato{(R)-(+)-5,5’-bis[di(3,5-xylyl) Me Me 250mg phosphino]-4,4’-bi-1,3-benzodioxole} Me 1g O Me ruthenium(II) Ru(OAc)2[(R)-dm-segphos®] 5g O (944450‑49‑1) P Me O O C50H50O8P2Ru; FW: 941.95; Ru yellow to brownish‑red to dark green solid; O O P Me m.p. >100° dec. O air sensitive O Me Note: Sold in collaboration with Takasago. Me Me Me Takasago SEGPHOS® Ru Catalyst Kit component. Technical Notes: 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM-SEGPHOS® ligand, as the ruthenium complex, gives superior enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of α-substituted-β-ketoesters. See 15-0066 2. Ruthenium catalyzed enantioselective synthesis of β amino acids by hydrogenation. 0.1 mol% Ruthenium complex O O NH2 O 0.2 mol% L, NH OAc, dioxane, 4 Tech. Note (2) H2 30 atm. 85° C, 8 hr Ref. (1) OCH3 OCH3 87%, 94% ee References: 1. US. Pat. 7626034.

44-017644-0176 Diacetato{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3-benzodioxole} 250mg

ruthenium(II) Ru(OAc)2[(S)-dm-segphos®] (944450‑50‑4) 1g

C50H50O8P2Ru; FW: 941.95; yellow to brownish‑red to dark green solid; m.p. >100° dec. 5g air sensitive Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit component. Technical Note: 1. See 44-0174 (page 32)

44-016444-0164 Diacetato{(R)-(+)-2,2’-bis[di(3,5-xylyl) Me 250mg phosphino]-1,1’-binaphthyl}ruthenium(II) Me Me 1g (374067‑50‑2) 5g Ru(OAc)2[(R)-xylbinap] Me C H O P Ru; FW: 954.04; dark brown pwdr.; 56 54 4 2 P Me m.p. >100° dec. O O air sensitive Ru O Note: Sold in collaboration with Takasago. P Me O Takasago BINAP Ru Acetate Catalyst Kit Me component. Technical Note: Me Me 1. Catalyst system used for asymmetric hydrogenation. Me

44-016544-0165 Diacetato{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl} 250mg

ruthenium(II) Ru(OAc)2[(S)-xylbinap] (374067‑49‑9) 1g

C56H54O4P2Ru; FW: 954.04; dark brown pwdr.; m.p. >100° dec. 5g air sensitive Note: Sold in collaboration with Takasago. Takasago BINAP Ru Acetate Catalyst Kit component. Technical Note: 1. See 44-0164 (page 32)

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44-016344-0163 Diacetato[(S)-(-)-2,2’-bis(di-p-tolylphosphino)-1,1’-binaphthyl] 250mg 44-021444-0214 Dichloro{(R)-(+)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg ruthenium(II) Ru(OAc)2[(S)-tolbinap] (106681‑15‑6) 1g benzodioxole}[(2R)-(-)-1,1-bis(4-methoxyphenyl)-3-methyl-1,2- 1g C52H46O4P2Ru; FW: 897.94; brown pwdr.; m.p. >100° dec. 5g butanediamine]ruthenium(II) Me 5g Me air sensitive RuCl2[(R)-dm-segphos®][(R)-daipen] Me Note: Sold in collaboration with Takasago. Takasago BINAP Ru Acetate (944450‑43‑5) O Catalyst Kit component. C H Cl N O P Ru; FW: 1209.18; H H 65 70 2 2 6 2 P Me H yellow pwdr. O Cl N iPr 44-017444-0174 Diacetato{(R)-(+)-5,5’-bis[di(3,5-xylyl) 250mg Me Me Ru phosphino]-4,4’-bi-1,3-benzodioxole} Me 1g air sensitive OMe O Me O Cl N 5g Note: Sold in collaboration with P Me ruthenium(II) Ru(OAc)2[(R)-dm-segphos®] H H (944450‑49‑1) O Takasago. Takasago SEGPHOS® Ru O P Me O C H O P Ru; FW: 941.95; O Catalyst Kit component. Me 50 50 8 2 Ru O Technical Note: Me yellow to brownish‑red to dark green solid; O Me OMe P MeO 1. Efficient catalyst for asymmetric hydrogenation of simple ketones. m.p. >100° dec. air sensitive O Me 44-021544-0215 Dichloro{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3-benzodioxole} 250mg Note: Sold in collaboration with Takasago. Me [(2S)-(+)-1,1-bis(4-methoxyphenyl)-3-methyl-1,2-butanediamine] 1g Me Me Takasago SEGPHOS® Ru Catalyst Kit ruthenium(II) RuCl2[(S)-dm-segphos®][(S)-daipen] (944450‑44‑6) 5g component. C65H70Cl2N2O6P2Ru; FW: 1209.18; yellow pwdr. Technical Notes: air sensitive 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM-SEGPHOS® ligand, as the ruthenium Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst complex, gives superior enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of Kit component. α-substituted-β-ketoesters. See 15-0066 Technical Note: 2. Ruthenium catalyzed enantioselective synthesis of β amino acids by hydrogenation. 1. See 44-0214 (page 33)

0.1 mol% Ruthenium complex 44-022844-0228 Dichloro{(R)-(+)-5,5’-bis[di(3,5-xylyl) Me 250mg O O NH2 O phosphino]-4,4’-bi-1,3-benzodioxole} Me Me 1g 0.2 mol% L, NH4OAc, dioxane, Tech. Note (2) [(1R,2R)-(+)-1,2-diphenylethylenediamine] O 5g H2 30 atm. 85° C, 8 hr Ref. (1) OCH3 OCH3 ruthenium(II) RuCl2[(R)-dm-segphos®] H H P Me Ph 87%, 94% ee [(R,R)-dpen] (944450‑45‑7) O Cl N C H Cl N O P Ru; FW: 1075.04; Ru References: 60 60 2 2 4 2 yellow pwdr. O P Cl N 1. US. Pat. 7626034. Me Ph air sensitive H H

44-017644-0176 Diacetato{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3-benzodioxole} 250mg Note: Sold in collaboration with Takasago. O ruthenium(II) Ru(OAc) [(S)-dm-segphos®] (944450‑50‑4) 1g Takasago SEGPHOS® Ru Catalyst Kit Me Me 2 Me C50H50O8P2Ru; FW: 941.95; yellow to brownish‑red to dark green solid; m.p. >100° dec. 5g component. air sensitive Technical Note: Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit 1. Efficient catalyst for asymmetric hydrogenation of simple ketones. component. 44-022944-0229 Dichloro{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg Technical Note: benzodioxole}[(1S,2S)-(-)-1,2-diphenylethylenediamine]ruthenium(II) 1g 1. See 44-0174 (page 32) RuCl2[(S)-dm-segphos®][(S,S)-dpen] (944450‑46‑8) 5g

44-016444-0164 Diacetato{(R)-(+)-2,2’-bis[di(3,5-xylyl) Me 250mg C60H60Cl2N2O4P2Ru; FW: 1075.04; yellow pwdr. phosphino]-1,1’-binaphthyl}ruthenium(II) Me Me 1g air sensitive (374067‑50‑2) 5g Ru(OAc)2[(R)-xylbinap] Me Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru C H O P Ru; FW: 954.04; dark brown pwdr.; Catalyst Kit component. 56 54 4 2 P Me m.p. >100° dec. O Technical Note: O air sensitive Ru 1. See 44-0228 (page 33) O Note: Sold in collaboration with Takasago. P Me O 44-021244-0212 Dichloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl} 250mg Takasago BINAP Ru Acetate Catalyst Kit Me [(2R)-(-)-1,1-bis(4-methoxyphenyl)-3-methyl-1,2-butanediamine] 1g component. ruthenium(II) RuCl [(R)-xylbinap][(R)-daipen] (220114‑32‑9) 5g Technical Note: Me Me 2 Me C71H74Cl2N2O2P2Ru; FW: 1221.28; Me 1. Catalyst system used for asymmetric hydrogenation. Me yellow to dark brown or green solid Me

44-016544-0165 Diacetato{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl} 250mg air sensitive H H (374067‑49‑9) 1g H ruthenium(II) Ru(OAc)2[(S)-xylbinap] Note: Sold in collaboration with Takasago. Cl N iPr P Me C56H54O4P2Ru; FW: 954.04; dark brown pwdr.; m.p. >100° dec. 5g Takasago BINAP Ru Diamine Catalyst Kit Ru OMe air sensitive component. P Me Cl N Note: Sold in collaboration with Takasago. Takasago BINAP Ru Acetate Technical Notes: H H Catalyst Kit component. 1. Highly active catalyst for hydrogenation of simple Me Technical Note: ketones giving high enantioselectivity when sterically Me 1. See 44-0164 (page 32) unsymmetrical ketones such as acetophenone, Me OMe

heteroaryl ketones, benzophenones, cyclopropyl ketones, and cyclohexyl ketones are substrates. Ee’s are enhanced with XylBINAP relative to BINAP. The otherwise poorly bonded ketone is held in the transition state by hydrogen bonding to the protic bidentate amine. 2. Carbonyl groups are selectively reduced even when olefins exist in the same molecule.

33 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds) 44-0212 Dichloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}[(2R)-(-)-1,1-bis(4-me-

(continued) thoxyphenyl)-3-methyl-1,2-butanediamine]ruthenium(II) RuCl2[(R)-xylbinap][(R)-daipen] (220114‑32‑9) 3. In the presence of strong base, and catalyst, simple ketones, having substituents at the α-position, may be induced to undergo dynamic kinectic resolution during their hydrogenation to produce two chiral carbon centers in high yield.

O 0.001 mol% (S,S)-cat., OH IPA, KOC(CH ) 3 3 Tech. Note (1) + H2 Ref. (1-4) Ph 8 atm, rt 60 hr Ph 97%, 99% ee

O 0.05 mol% (S,S)-cat., OH IPA, K2CO3 Tech. Note (2) + H2 Ref. (4) 8 atm, rt 15 hr 98%, 97% ee

O OH

NHCO2C(CH3)3 0.33 mol% (R,S)cat., NHCO2C(CH3)3 KOH, i-PrOH Tech. Note (3) Ref. (5) H2 8 Atm, rt 5 hr

98%, 82% ee References: 1. Angew Chem. Int. Ed., 2001, 40, 40, review, article 2. Org. Lett., 2000, 2, 1749 3. Org. Lett., 2000, 2, 659 4. J. Am. Chem. Soc., 1998, 120, 13529 5. J. Am. Chem. Soc., 2000, 122, 6510

44-021344-0213 Dichloro{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}[(2S)- 250mg (+)-1,1-bis(4-methoxyphenyl)-3-methyl-1,2-butanediamine]ruthenium(II) 1g

RuCl2[(S)-xylbinap][(S)-daipen] (220114‑01‑2) 5g

C71H74Cl2N2O2P2Ru; FW: 1221.28; orange pwdr. air sensitive Note: Sold in collaboration with Takasago. Takasago BINAP Ru Diamine Catalyst Kit component. Technical Note: 1. See 44-0212 (page 33)

44-022644-0226 Dichloro{(R)-(+)-2,2’-bis[di(3,5-xylyl) Me Me 250mg phosphino]-1,1’-binaphthyl}[(1R,2R)-(+)- Me 1g 1,2-diphenylethylenediamine]ruthenium(II) 5g P H H RuCl2[(R)-xylbinap][(R,R)-dpen] Me Cl N Ph (220114‑38‑5) Ru C66H64Cl2N2P2Ru; FW: 1119.15; yellow pwdr. MeCl N air sensitive P H H Ph Note: Sold in collaboration with Takasago. Takasago BINAP Ru Diamine Catalyst Kit Me Me Me component. Technical Notes: 1. See 44-0210. 2. Sequential asymmetric hydrogenation reactions with solution or polymer-bound BINAP/Diamine complexes. 3. Asymmetic hydrogenation of imines. 4. Catalysts for deracemization of benzylic alcohols.

Visit strem.com for new product announcements. 34 RUTHENIUM (Compounds) 44-0226 Dichloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}[(1R,2R)-(+)-1,2-

(continued) diphenylethylenediamine]ruthenium(II) RuCl2[(R)-xylbinap][(R,R)-dpen] (220114‑38‑5) O Me HO Me 3. In the presence of strong base, and catalyst, simple ketones, having substituents at the α-position, may Polymer-bound Tech. Note (2) be induced to undergo dynamic kinectic resolution during their hydrogenation to produce two chiral carbon or solution Ref. (1,2) centers in high yield.

O 0.001 mol% (S,S)-cat., OH IPA, KOC(CH ) H 3 3 Tech. Note (1) N H2, [Ru], + H2 N Ref. (1-4) t-BuOK Ph 8 atm, rt 60 hr Ph Tech. Note (3) Ref. (3) 97%, 99% ee N N H O 0.05 mol% (S,S)-cat., OH IPA, K CO OH OH 2 3 Tech. Note (2) Tech. Note (4) + H2 Ref. (4) 8 atm, rt 15 hr Ar R Ar R Ref. (4) 98%, 97% ee References: 1. Angew. Chem. Int. Ed., 2001, 40, 40 (review) O OH 2. Adv. Synth. Catal., 2001, 343, 369. 3. Adv. Synth. Catal., 2003, 345, 195. NHCO2C(CH3)3 0.33 mol% (R,S)cat., NHCO2C(CH3)3 4. Chem. Commun., 2007, 2608. KOH, i-PrOH Tech. Note (3) Ref. (5) 44-022444-0224 Dichloro{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}[(1S,2S)-(-)- 250mg H2 8 Atm, rt 5 hr 1,2-diphenylethylenediamine]ruthenium(II) RuCl2[(S)-xylbinap][(S,S)-dpen] 1g (220114‑03‑4) 5g 98%, 82% ee C66H64Cl2N2P2Ru; FW: 1119.15; yellow pwdr. air sensitive References: Note: Sold in collaboration with Takasago. Takasago BINAP Ru Diamine Catalyst Kit 1. Angew Chem. Int. Ed., 2001, 40, 40, review, article component. 2. Org. Lett., 2000, 2, 1749 Technical Note: 3. Org. Lett., 2000, 2, 659 1. See 44-0226 (page 34) 4. J. Am. Chem. Soc., 1998, 120, 13529 44-052044-0520 Dimethylammonium dichlorotri(µ-chloro)bis{(R)-(+)-5,5’-bis[di(3,5- 250mg 5. J. Am. Chem. Soc., 2000, 122, 6510 xylyl)phosphino]-4,4’-bi-1,3-benzodioxole}diruthenate(II) [NH2Me2] 1g

44-021344-0213 Dichloro{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}[(2S)- 250mg [{RuCl((R)-dm-segphos®)} (µ-Cl) ] (935449‑46‑0) 2 3 -1 5g 1g (CH ) NH +[C H Cl O P Ru ]-; (+)-1,1-bis(4-methoxyphenyl)-3-methyl-1,2-butanediamine]ruthenium(II) 3 2 2 92 88 5 8 4 2 O O RuCl2[(S)-xylbinap][(S)-daipen] (220114‑01‑2) 5g FW: 1870.06; light brown pwdr.; Xyl Xyl m.p. >100° dec. Xyl Cl Cl Xyl C71H74Cl2N2O2P2Ru; FW: 1221.28; orange pwdr. O P P O air sensitive air sensitive Ru Cl Ru O P P O Note: Sold in collaboration with Takasago. Takasago BINAP Ru Diamine Note: Sold in collaboration with Xyl Cl Cl Xyl Catalyst Kit component. Takasago. Takasago SEGPHOS® Xyl Xyl O O Technical Note: Ru Catalyst Kit component. + Me2NH2 1. See 44-0212 (page 33) Technical Notes: 1. Biaryl bisphosphine ligand with narrow dihedral angle. The DM-SEGPHOS ligand, as the ruthenium

44-022644-0226 Dichloro{(R)-(+)-2,2’-bis[di(3,5-xylyl) Me Me 250mg complex, gives superior enantioselectivity and diastereoselectivity in the asymmetric hydrogenation of phosphino]-1,1’-binaphthyl}[(1R,2R)-(+)- Me 1g α-substituted-β-ketoesters. See 15-0066. 1,2-diphenylethylenediamine]ruthenium(II) 5g 2. Ruthenium catalyzed enantioselective synthesis of β amino acids by hydrogenation. P H H 3. Ruthenium catalyzed asymmetric hydrogenation of 3-quinuclidinone. See 44-0098 for Ru catalyst. RuCl2[(R)-xylbinap][(R,R)-dpen] Me Cl N Ph (220114‑38‑5) Ru O O 0.1 mol% [RuCl (p-cymene)] NH2 O C66H64Cl2N2P2Ru; FW: 1119.15; yellow pwdr. MeCl N 2 2 P Ph air sensitive H H 0.2 mol% L, NH4OAc, dioxane, Tech. Note (2) Note: Sold in collaboration with Takasago. OCH3 H2 30 atm. 85°, 8 h, C OCH3 Ref. (1) Takasago BINAP Ru Diamine Catalyst Kit Me Me Me 87%, 94% ee component. Technical Notes: 1. See 44-0210. 0.1% (LRuCyCl)+Cl-, 2. Sequential asymmetric hydrogenation reactions with solution or polymer-bound BINAP/Diamine complexes. O 0.4% (R)-DAIPEN OH 3. Asymmetic hydrogenation of imines. Tech. Note (3) + H2 4. Catalysts for deracemization of benzylic alcohols. N IPA/t-BuOK N Ref. (2) 30 Atm ,C, 30° 15 hr 99%, 91% ee References: 1. U.S. Pat. 7626034. 2. U.S. Pat 7462722.

35 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds)

44-052144-0521 Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-5,5’-bis[di(3,5- 250mg

xylyl)phosphino]-4,4’-bi-1,3-benzodioxole}diruthenate(II) [NH2Me2] 1g

[{RuCl((S)-dm-segphos®)}2(µ-Cl)3] (944451‑14‑3) 5g + - (CH3)2NH2 [C92H88Cl5O8P4Ru2] ; FW: 1870.06; light brown pwdr.; m.p. >100° dec. air sensitive Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit component. Technical Note: 1. See 44-0520 (page 35)

44-051444-0514 Dimethylammonium dichlorotri(µ-chloro)bis{(R)-(+)-2,2’-bis[di(3,5- 250mg

xylyl)phosphino]-1,1’-binaphthyl}diruthenate(II) [NH2Me2][{Ru- 1g

Cl((R)-xylbinap)}2(µ-Cl)3] (944451‑08‑5) 5g + - (CH3)2NH2 [C104H96Cl5P4Ru2] ; -1 FW: 1894.26; red‑brown pwdr.; m.p. >100° dec. Xyl Xyl Xyl Cl Cl Xyl air sensitive P P Ru Cl Ru Note: Sold in collaboration with P P Takasago. Takasago BINAP Ru Xyl Cl Cl Xyl Dimer Catalyst Kit component. Xyl Xyl Technical Note: + 1. Catalyst system for asymmetric Me2NH2 hydrogenation.

44-051544-0515 Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-2,2’-bis[di(3,5-xylyl)phos- 250mg

phino]-1,1’-binaphthyl}diruthenate(II) [NH2Me2][{RuCl((S)-xylbinap)}2(µ-Cl)3] 1g (944451‑10‑9) 5g + - (CH3)2NH2 [C104H96Cl5P4Ru2] ; FW: 1894.26; red‑brown pwdr.; m.p. >100° dec. air sensitive Note: Sold in collaboration with Takasago. Takasago BINAP Ru Dimer Catalyst Kit component. Technical Note: 1. See 44-0514 (page 36)

44-051844-0518 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-5,5’- 250mg bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole]diruthenate(II) 1g

[NH2Me2][{RuCl((R)-segphos®)}2(µ-Cl)3] (346457‑41‑8) 5g + - (CH3)2NH2 [C76H48Cl5O8P4Ru2] ; -1 FW: 1637.57; light brown pwdr.; O O m.p. >100° dec. Ph Ph Ph Cl Cl Ph air sensitive O P P O Note: Sold in collaboration with Ru Cl Ru P P Takasago. Takasago SEGPHOS® O Ph Ph O Ph Cl Cl Ph Ru Catalyst Kit component. O O Me NH + Technical Notes: 2 2 1. Highly enantioselective, highly active catalyst for hydrogenation of functionalized ketones. The chlororuthenate salts show catalytic activity at relatively low temperature. See 15-0136 . 2. Catalyst for enantioselective hydrogenation of enamines. O OH Ru, H2 OEt OEt Tech. Note (1) Ph Ph Ref. (1) O O

CO Me CO Me 2 Ru, H 2 2 Tech. Note (2) Ar Ar N R N R Ref. (2) H H References: 1. Adv. Synth. Catal., 2001, 343, 264 2. U.S. Pat. 8188307.

Visit strem.com for new product announcements. 36 RUTHENIUM (Compounds)

44-052144-0521 Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-5,5’-bis[di(3,5- 250mg 44-051944-0519 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-5,5’- 250mg xylyl)phosphino]-4,4’-bi-1,3-benzodioxole}diruthenate(II) [NH2Me2] 1g bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole]diruthenate(II) 1g

[{RuCl((S)-dm-segphos®)}2(µ-Cl)3] (944451‑14‑3) 5g [NH2Me2][{RuCl((S)-segphos®)}2(µ-Cl)3] (488809‑34‑3) 5g + - + - (CH3)2NH2 [C92H88Cl5O8P4Ru2] ; FW: 1870.06; light brown pwdr.; (CH3)2NH2 [C76H48Cl5O8P4Ru2] ; FW: 1637.57; light brown pwdr.; m.p. >100° dec. m.p. >100° dec. air sensitive air sensitive Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Note: Sold in collaboration with Takasago. Takasago SEGPHOS® Ru Catalyst Kit component. Catalyst Kit component. Technical Note: Technical Note: 1. See 44-0520 (page 35) 1. See 44-0518 (page 36)

44-051444-0514 Dimethylammonium dichlorotri(µ-chloro)bis{(R)-(+)-2,2’-bis[di(3,5- 250mg 44-051044-0510 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2’- 250mg xylyl)phosphino]-1,1’-binaphthyl}diruthenate(II) [NH2Me2][{Ru- 1g bis(diphenylphosphino)-1,1’-binaphthyl]diruthenate(II) [NH2Me2] 1g (944451‑08‑5) 5g 5g Cl((R)-xylbinap)}2(µ-Cl)3] [{RuCl((R)-binap)}2(µ-Cl)3] -1 + - (CH3)2NH2 [C104H96Cl5P4Ru2] ; -1 (199684‑47‑4) FW: 1894.26; red‑brown pwdr.; (CH ) NH +[C H Cl P Ru ]-; 3 2 2 88 64 5 4 2 Ph Cl Ph m.p. >100° dec. Xyl Xyl FW: 1669.83; orange pwdr.; Ph Cl Ph Xyl Cl Cl Xyl P P air sensitive P P m.p. >100° dec. Ru Cl Ru P P Note: Sold in collaboration with Ru Cl Ru air sensitive Ph Ph P P Ph Cl Cl Ph Takasago. Takasago BINAP Ru Xyl Cl Cl Xyl Note: Sold in collaboration with Dimer Catalyst Kit component. Xyl Xyl Takasago. Takasago BINAP Ru + Me2NH2 Technical Note: Dimer Catalyst Kit component. + 1. Catalyst system for asymmetric Me2NH2 44-051144-0511 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2’- 250mg hydrogenation. bis(diphenylphosphino)-1,1’-binaphthyl]diruthenate(II) [NH2Me2][{RuCl((S)- 1g

44-051544-0515 Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-2,2’-bis[di(3,5-xylyl)phos- 250mg binap)}2(µ-Cl)3] (199541‑17‑8) 5g + - phino]-1,1’-binaphthyl}diruthenate(II) [NH2Me2][{RuCl((S)-xylbinap)}2(µ-Cl)3] 1g (CH3)2NH2 [C88H64Cl5P4Ru2] ; FW: 1669.83; orange pwdr.; m.p. >100° dec. (944451‑10‑9) 5g air sensitive + - (CH3)2NH2 [C104H96Cl5P4Ru2] ; FW: 1894.26; red‑brown pwdr.; m.p. >100° dec. Note: Sold in collaboration with Takasago. Takasago BINAP Ru Dimer Catalyst air sensitive Kit component.

Note: Sold in collaboration with Takasago. Takasago BINAP Ru Dimer Catalyst Kit 44-051644-0516 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2’- 50mg component. bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl] 250mg Technical Note: diruthenate(II) [NH2Me2][{RuCl((R)-H8-binap)}2(µ-Cl)3] (204933‑84‑6) 1. See 44-0514 (page 36) + - -1 (CH3)2NH2 [C88H80Cl5P4Ru2] ;

44-051844-0518 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-5,5’- 250mg FW: 1685.96; red‑brown pwdr.; Ph Ph bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole]diruthenate(II) 1g m.p. >100° dec. Ph Cl Cl Ph P P [NH2Me2][{RuCl((R)-segphos®)}2(µ-Cl)3] (346457‑41‑8) 5g air sensitive Ru Cl Ru (CH ) NH +[C H Cl O P Ru ]-; -1 Note: Sold in collaboration with P P 3 2 2 76 48 5 8 4 2 Ph Ph FW: 1637.57; light brown pwdr.; O O Takasago. Ph Cl Cl Ph m.p. >100° dec. Ph Ph Technical Notes: Ph Cl Cl Ph air sensitive O P P O 1. Biaryl bisphosphine ligand. The H8-BINAP Note: Sold in collaboration with Ru Cl Ru ligand, as the ruthenium complex, catalyzes P P Me NH + Takasago. Takasago SEGPHOS® O Ph Ph O hydrogenation of unsaturated carboxylic acids 2 2 Ph Cl Cl Ph Ru Catalyst Kit component. to a higher ee than does BINAP. (Ref. 1,2) O O 2. The ruthenium catalyzed hydrogenation of aryl propenoic acid to produce the drug Ibuprofen. Me NH + Technical Notes: 2 2 1. Highly enantioselective, highly active catalyst for hydrogenation of functionalized ketones. The chlororuthenate salts show catalytic activity at relatively low temperature. See 15-0136 . 0.5 mol% 2. Catalyst for enantioselective hydrogenation of enamines. [(S)-L]Ru(OAc)2 100 atm H2, MeOH, Tech. Note (1,2) O OH 8 h, rt Ref. (1,2) Ru, H2 OEt OEt Tech. Note (1) Ph Ph Ref. (1) COOH COOH O O 97%, 97%ee References: CO2Me CO2Me 1. J. Org. Chem., , 61, 5510 Ru, H 1996 2 Tech. Note (2) 2. Topics Organometal. Chem. 2004, 6, 63, review Ar Ar N R N R Ref. (2) H H References: 1. Adv. Synth. Catal., 2001, 343, 264 2. U.S. Pat. 8188307.

37 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds)

44-051744-0517 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2’- 50mg bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl] 250mg diruthenate(II) [NH2Me2][{RuCl((S)-H8-binap)}2(µ-Cl)3] (944451‑12‑1) + - (CH3)2NH2 [C88H80Cl5P4Ru2] ; FW: 1685.96; red‑brown pwdr.; m.p. >100° dec. air sensitive Note: Sold in collaboration with Takasago. Technical Note: 1. Catalyst system for asymmetric hydrogenation. References: 1. World Patent WO2003/0307676

44-051244-0512 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2’-bis(di-p-tolylphos- 250mg

phino)-1,1’-binaphthyl]diruthenate(II) [NH2Me2][{RuCl((R)-tolbinap)}2(µ-Cl)3] 1g (749935‑02‑2) -1 5g (CH ) NH +[C H Cl P Ru ]-; 3 2 2 96 80 5 4 2 o-tol o-tol FW: 1782.05; brown pwdr.; o-tol m.p. >100° dec. o-tol Cl Cl P P air sensitive Ru Cl Ru Note: Sold in collaboration with P P Takasago. Takasago BINAP Cl Cl o-tol o-tol Ru Dimer Catalyst Kit o-tol o-tol component. Me NH + Technical Note: 2 2 1. Catalyst system for asymmetric hydrogenation. References: 1. World Patent WO2004/074255

44-051344-0513 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2’-bis(di-p-tolylphosphino)- 250mg

1,1’-binaphthyl]diruthenate(II) [NH2Me2][{RuCl((S)-tolbinap)}2(µ-Cl)3] (309735‑86‑2) 1g + - (CH3)2NH2 [C96H80Cl5P4Ru2] ; FW: 1782.05; brown pwdr.; m.p. >100° dec. 5g air sensitive Note: Sold in collaboration with Takasago. Takasago BINAP Ru Dimer Catalyst Kit component. Technical Note: 1. See 44-0512 (page 38)

44-018544-0185 N-[(1R,2R)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethyl- Me 250mg amino)-ethyl]-4-methylbenzene sulfonamide(chloro) 1g ruthenium(II) (R,R)-Ts-DENEB® (1333981‑84‑2) 5g Me C31H33ClN2O3RuS; FW: 650.19; gray to brown solid Note: Sold in collaboration with Takasago. O O S Ru US. Patent 9079931. N Cl Technical Notes: O N 1. Catalyst used for asymmetric -transfer hydrogenation. Ph H 2. Catalyst used for asymmetric H2 – hydrogenation. Ph 3. Catalyst used for dynamic kinetic resolution. 4. Catalyst used for asymmetric transfer hydrogenation of unsymmetrical benzophenones. 5. Catalyst used for asymmetric transfer hydrogenation of Aryl N-Heteroaryl Ketones. 6. Catalyst used for asymmetric transfer hydrogenation of alpha-Substituted Ketone. O OH (R,R)-Ru-cat + HCO2H/Et3N = 5/2 R R' (2M) 60°C R R'

O O O Cl

HO Tech. Note (1) (S/C=30,000, 96h) (S/C=1,000, 5h) (S/C=500, 24h) Ref. (1) 95% conv. 97% ee >99% conv. 97% ee >99% conv. 95% ee (>95% select.) O O O CN OH

OMe

(S/C=1,000, 5h) (S/C=1,000, 24h) (S/C=1,000, 5h) >99% conv. 95% ee >99% conv. 93% ee 98% conv. 96% ee

Visit strem.com for new product announcements. 38 RUTHENIUM (Compounds)

44-051744-0517 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2’- 50mg 44-0185 N-[(1R,2R)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethylamino)-ethyl]-4-methylbenzene bis(diphenylphosphino)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphthyl] 250mg (continued) sulfonamide(chloro)ruthenium(II) (R,R)-Ts-DENEB® (1333981‑84‑2) diruthenate(II) [NH2Me2][{RuCl((S)-H8-binap)}2(µ-Cl)3] (944451‑12‑1) + - O (CH3)2NH2 [C88H80Cl5P4Ru2] ; FW: 1685.96; red‑brown pwdr.; m.p. >100° dec. OH air sensitive (R,R)-Ru-cat + H2 Note: Sold in collaboration with Takasago. (3 MPa) Technical Note: R R' MeOH, 60°C R R' 1. Catalyst system for asymmetric hydrogenation. References: O O Tech. Note (2) 1. World Patent WO2003/0307676 Ref. (1) OH

44-051244-0512 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2’-bis(di-p-tolylphos- 250mg O phino)-1,1’-binaphthyl]diruthenate(II) [NH2Me2][{RuCl((R)-tolbinap)}2(µ-Cl)3] 1g (749935‑02‑2) -1 5g (S/C=1,000, 20h) (S/C=5,000, 18h) (CH ) NH +[C H Cl P Ru ]-; 3 2 2 96 80 5 4 2 o-tol o-tol >99% conv. 99% ee >99% conv. 93% ee FW: 1782.05; brown pwdr.; o-tol m.p. >100° dec. o-tol Cl Cl air sensitive P P O OH Ru Cl Ru (R,R)-Ru-cat Note: Sold in collaboration with P P Takasago. Takasago BINAP Cl Cl Ph + HCO2H/Et3N = 5/2 Ph o-tol o-tol Ru Dimer Catalyst Kit o-tol Ph (2M) DMF, 60°C Ph o-tol Tech. Note (3) component. Ref. (1) Me NH + Technical Note: 2 2 O (S/C=10,000, 24h) OH 1. Catalyst system for asymmetric hydrogenation. >99% conv. (dl:meso = 97.2:2.8) References: >99% ee (dl) 1. World Patent WO2004/074255

44-051344-0513 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2’-bis(di-p-tolylphosphino)- 250mg O (R,R)-Ru-cat 1 mol% OH * 1,1’-binaphthyl]diruthenate(II) [NH2Me2][{RuCl((S)-tolbinap)}2(µ-Cl)3] (309735‑86‑2) 1g + HCOOH/Et3N + - Ar Ar' Ar Ar' (CH3)2NH2 [C96H80Cl5P4Ru2] ; FW: 1782.05; brown pwdr.; m.p. >100° dec. 5g air sensitive Note: Sold in collaboration with Takasago. Takasago BINAP Ru Dimer Catalyst Kit component. O Technical Note: CH O Cl O 3 F 1. See 44-0512 (page 38)

44-018544-0185 N-[(1R,2R)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethyl- Me 250mg F amino)-ethyl]-4-methylbenzene sulfonamide(chloro) 1g F Tech. Note (4) ruthenium(II) (R,R)-Ts-DENEB® (1333981‑84‑2) o o 5g (60 C, 18 h) (40 C, 17 h) (30 oC, 16 h) C H ClN O RuS; FW: 650.19; gray to brown solid Me Ref. (2) 31 33 2 3 98% yield. 98% ee >99% yield. 98% ee Note: Sold in collaboration with Takasago. O >99% yield. 95% ee O S Ru US. Patent 9079931. N Cl Technical Notes: O O N O 1. Catalyst used for asymmetric -transfer hydrogenation. Ph H O2N O2N 2. Catalyst used for asymmetric H2 – hydrogenation. Ph 3. Catalyst used for dynamic kinetic resolution. S 4. Catalyst used for asymmetric transfer hydrogenation of unsymmetrical benzophenones. NO2 5. Catalyst used for asymmetric transfer hydrogenation of Aryl N-Heteroaryl Ketones. o o 6. Catalyst used for asymmetric transfer hydrogenation of alpha-Substituted Ketone. (30 C, 26 h) (10 C, 8 h) 90% yield. >99% ee 96% yield. 98% ee O OH (R,R)-Ru-cat O O- OH + HCO2H/Et3N = 5/2 (R,R)-Ru-cat 5 mol% N+ Zn * N R R' (2M) 60°C R R' HCOONa H O/DMSO Tech. Note (5) O O 2 NH4Cl R O R o Cl 50 C, 24 h Ref. (3) R=H : 86% yield. 97.8% ee HO R=Cl : 92% yield. 99.8% ee Tech. Note (1) (S/C=30,000, 96h) (S/C=1,000, 5h) (S/C=500, 24h) Ref. (1) 95% conv. 97% ee >99% conv. 97% ee >99% conv. 95% ee (>95% select.) O O O CN OH

OMe

(S/C=1,000, 5h) (S/C=1,000, 24h) (S/C=1,000, 5h) >99% conv. 95% ee >99% conv. 93% ee 98% conv. 96% ee

39 [email protected] . [email protected] . [email protected] . [email protected] RUTHENIUM (Compounds) 44-0185 N-[(1R,2R)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethylamino)-ethyl]-4-methylbenzene (continued) sulfonamide(chloro)ruthenium(II) (R,R)-Ts-DENEB® (1333981‑84‑2)

O (R,R)-Ru-cat (S/C=1,000) OH X X HCO2H/HCO2K R R * EtOAc/H2O 60 oC

Tech. Note (6) O O O Ref. (4) Br Br Br

AcO F3C

(4 h) (6 h) (4 h) 93% yield. 96% ee 93% yield. 95% ee 94% yield. 94% ee References: 1. J. Am. Chem.Soc., 2011, 133, 14960 2. J. Am. Chem. Soc. 2016, 138, 10084. 3. Org. Lett. 2017, 19. 2094. 4. Adv. Synth. Catal. 2017, 360, 568

44-018644-0186 N-[(1S,2S)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethylamino)-eth- 250mg yl]-4-methylbenzene sulfonamide(chloro)ruthenium(II) (S,S)-Ts-DENEB® 1g (1384974‑37‑1) 5g

C31H33ClN2O3RuS; FW: 650.19; gray to brown solid Note: Sold in collaboration with Takasago. US Pat. 9217005, US Pat. 9073827. Technical Note: 1. See 44-0185 (page 38)

96-6955 Takasago ATH (Asymmetric Transfer Hydrogenation) Catalyst Kit See page 42

96-6953 Takasago BINAP Ru Acetate Catalyst Kit See page 44

96-6951 Takasago BINAP Ru Cymene Catalyst Kit See page 45

96-6954 Takasago BINAP Ru Diamine Catalyst Kit See page 46

96-6952 Takasago BINAP Ru Dimer Catalyst Kit See page 47

96-6901 Takasago SEGPHOS® Ru Catalyst Kit See page 49 ZINC (Compounds)

30-405030-4050 Oxo[hexa(trifluoroacetato)]tetrazinc F C CF3 5g 3 O O trifluoroacetic acid adduct ZnTAC24™ 25g (1299489‑47‑6) Zn O O Zn4(CF3COO)6(O)(CF3COOH)·; FW: 955.65; O white solid Zn O Zn moisture sensitive F3C O Note: Sold in collaboration with Takasago. O O US. Pat. 7888513 and 8552204. O O Technical Notes: Zn CF3 F3C O O 1. Zinc-catalyzed transesterification of various methyl esters under CF3 mild conditions 2. Zinc-catalyzed acylation of alcohols in the presence of amines 3. Zinc-catalyzed cycloizomerization. Synthesis of substituted furanes and furopyrimidine nucleosides

Visit strem.com for new product announcements. 40 ZINC (Compounds)

30-4050 Oxo[hexa(trifluoroacetato)]tetrazinc trifluoroacetic acid adduct ZnTAC24™ (1299489‑47‑6) (continued) O OH Zn-Cluster (R,R)-Ru-cat (S/C=1,000) O O X X H (1.25 mol%) H Tech. Note (1) HCO2H/HCO2K N + HO N R R * Cbz OMe PhCl Cbz O Ref. (1) EtOAc/H2O reflux, 18h 99% 60 oC Zn-Cluster Tech. Note (6) (1.25 mol%) Tech. Note (2) O O O Ref. (4) H N OH + PhCOOMe H N OCOPh 2 PhCl 2 Ref. (2) Br Br Br reflux, 24h

AcO F3C H O N O O N O (4 h) (6 h) (4 h) Zn-Cluster 93% yield. 96% ee 93% yield. 95% ee 94% yield. 94% ee R N O (3.0 mol%) N O Tech. Note (3) References: DCE Ref. (3) 1. J. Am. Chem.Soc., , 133, 14960 R OAc OAc 2011 reflux, 30h 99% 2. J. Am. Chem. Soc. 2016, 138, 10084. OAc OAc 3. Org. Lett. 2017, 19. 2094. References: 4. Adv. Synth. Catal. 2017, 360, 568 1. J.Org. Chem., 2008, 73, 5147

44-018644-0186 N-[(1S,2S)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethylamino)-eth- 250mg 2. J. Am. Chem. Soc., 2008, 130, 2944 yl]-4-methylbenzene sulfonamide(chloro)ruthenium(II) (S,S)-Ts-DENEB® 1g 3. J.Org. Chem., 2008, 73, 5881 (1384974‑37‑1) 5g

C31H33ClN2O3RuS; FW: 650.19; gray to brown solid Note: Sold in collaboration with Takasago. US Pat. 9217005, US Pat. 9073827. Technical Note: 1. See 44-0185 (page 38)

96-6955 Takasago ATH (Asymmetric Transfer Hydrogenation) Catalyst Kit See page 42

96-6953 Takasago BINAP Ru Acetate Catalyst Kit See page 44

96-6951 Takasago BINAP Ru Cymene Catalyst Kit See page 45

96-6954 Takasago BINAP Ru Diamine Catalyst Kit See page 46

96-6952 Takasago BINAP Ru Dimer Catalyst Kit See page 47

96-6901 Takasago SEGPHOS® Ru Catalyst Kit See page 49 ZINC (Compounds)

41 [email protected] . [email protected] . [email protected] . [email protected] KITS - Takasago ATH (Asymmetric Transfer Hydrogenation) Catalyst Kit

96-695596-6955 Takasago ATH (Asymmetric Transfer Hydrogenation) Catalyst Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

Me Me F F F

F F O O O O O O Me S S Me S Me Ph N Ph N Me Ph N Ru Ru Me Ru iPr iPr Ph N Cl Ph N Cl Ph N Cl H H H H H H 44-0148 250mg 44-0154 250mg 44-0156 250mg RuCl[(R,R)-Tsdpen](p-cymene) RuCl[(R,R)-Tsdpen(mesitylene) RuCl[(R,R)-Fsdpen](p-cymene) 44-0149 44-0155 44-0157 RuCl[(S,S)-Tsdpen](p-cymene) RuCl[(S,S)-Tsdpen(mesitylene) RuCl[(S,S)-Fsdpen](p-cymene)

Me Me Me Me Me Me P O Me Cl H H O N OMe Me O Ru S Ru O S Ru H H N Cl N Cl Me N H P O N O iPr N Ph H Ph H Me Me Me MeO Ph Ph

44-0185 250mg 44-0217 250mg 44-0255 250mg (R,R)-Ts-DENEB™ (R)-RUCY™-XylBINAP Ru-(R,R)-Ms-DENEB 44-0186 44-0218 44-0256 (S,S)-Ts-DENEB™ (S)-RUCY™-XylBINAP Ru-(S,S)-Ms-DENEB

Visit strem.com for new product announcements. 42 KITS - Takasago ATH (Asymmetric Transfer Hydrogenation) Catalyst Kit 96-6955 Takasago ATH (Asymmetric Transfer Hydrogenation) Catalyst Kit (continued) 44-0148 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl] 250mg See page 23 (4-toluenesulfonyl)amido}(p-cymene)ruthenium(II), min. 95% RuCl[(R,R)-Tsdpen](p-cymene) (192139-92-7) 44-0149 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl] 250mg See page 22 (4-toluenesulfonyl)amido}(p-cymene)ruthenium(II), min. 90% RuCl[(S,S)-Tsdpen](p-cymene) (192139-90-5) 44-0154 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl] 250mg See page 24 (4-toluenesulfonyl)amido}(mesitylene)ruthenium(II), min. 90% RuCl[(R,R)-Tsdpen(mesitylene) (174813-82-2) 44-0155 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl] 250mg See page 24 (4-toluenesulfonyl)amido}(mesitylene)ruthenium(II), min. 90% RuCl[(S,S)-Tsdpen](mesitylene) (174813-81-1) 44-0156 Chloro{[(1R,2R)-(-)-2-amino-1,2-diphenylethyl](pentafluo- 250mg See page 22 rophenylsulfonyl)amido}(p-cymene)ruthenium(II), min. 90% RuCl[(R,R)-Fsdpen](p-cymene) (1026995-71-0) 44-0157 Chloro{[(1S,2S)-(+)-2-amino-1,2-diphenylethyl](pentafluo- 250mg See page 22 rophenylsulfonyl)amido}(p-cymene)ruthenium(II), min. 90% RuCl[(S,S)-Fsdpen](p-cymene) (1026995-72-1) 44-0185 N-[(1R,2R)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethylamino)- 250mg See page 38 ethyl]-4-methylbenzene sulfonamide(chloro)ruthenium(II) (R,R)-Ts-DENEB® (1333981-84-2) 44-0186 N-[(1S,2S)-1,2-Diphenyl-2-(2-(4-methylbenzyloxy)ethylamino)- 250mg See page 40 ethyl]-4-methylbenzene sulfonamide(chloro)ruthenium(II) (S,S)-Ts-DENEB® (1384974-37-1) 44-0217 Chloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 28 binaphthyl} [(2R)-(-)-1-(4-methoxyphenyl)- 1’-(4-methoxy phenyl-kC)-3- methyl-1,2-butanediamine]ruthenium(II) (R)-RUCY®XylBINAP (1384974-38-2) 44-0218 Chloro{(S)-(-)-2,2’-bis[di(3,5-xylyl) phosphino]-1,1’- 250mg See page 28 binaphthyl}[(2S)- (+)-1-(4-methoxyphenyl)-1’-(4- methoxyphenyl-kC)-3-methyl-1,2-butanediamine] ruthenium(II) (S)-RUCY®XylBINAP (1312713-89-5) 44-0255 Chloro{N-[(1R,2R)-2-[(S)-[2-[[1,2,3,4,5,6-η)-4-methylphenyl] 250mg See page 29 methoxy]ethyl]amino]-1,2-diphenylethylmethanesulfonamidato} ruthenium(II) (R,R)-Ms-DENEB® (1333981-86-4) 44-0256 Chloro{N-[(1S,2S)-2-[(R)-[2-[[1,2,3,4,5,6-η)-4-methylphenyl] 250mg See page 30 methoxy]ethyl]amino]-1,2-diphenylethylmethanesulfonamidato} ruthenium(II) (S,S)-Ms-DENEB® (1361318-83-3)

43 [email protected] . [email protected] . [email protected] . [email protected] KITS - Takasago BINAP Ligand Kit

96-695096-6950 Takasago BINAP Ligand Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

P Me PPh2 P(p-tolyl)2 2

PPh2 P Me P(p-tolyl)2

Me 2 250mg . . 250mg . 250mg 15-0150 (R)-(+)-BINAP 15-0152 (R)-(+)-TolBINAP 15-0476 (R)-(+)-XylBINAP 15-0151 (S)-(-)-BINAP 15-0153 (S)-(-)-TolBINAP 15-0477 (S)-(-)-XylBINAP

15-0150 (R)-(+)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% 250mg See page 5 (R)-(+)-BINAP (76189-55-4) 15-0151 (S)-(-)-2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl, 98% 250mg See page 9 (S)-(-)-BINAP (76189-56-5) 15-0152 (R)-(+)-2,2’-Bis(di-p-tolylphosphino)-1,1’-binaphthyl, 98% 250mg See page 12 (R)-(+)-TolBINAP (99646-28-3) 15-0153 (S)-(-)-2,2’-Bis(di-p-tolylphosphino)-1,1’-binaphthyl, 98% 250mg See page 13 (S)-(-)-TolBINAP (100165-88-6) 15-0476 (R)-(+)-2,2’-Bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl, 98% 250mg See page 17 (R)-(+)-XylBINAP (137219-86-4) 15-0477 (S)-(-)-2,2’-Bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl, 98% 250mg See page 18 (S)-(-)-XylBINAP (135139-00-3) KITS - Takasago BINAP Ru Acetate Catalyst Kit

96-695396-6953 Takasago BINAP Ru Acetate Catalyst Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

Me Me Me Me Me Me Me Me Ph Ph O O P Me O P P O O Ru Ru O Ru P O O O Ph P Ph O O P Me O Me Me Me Me Me Me Me Me 44-0152 250mg 44-0162 250mg 44-0164 250mg

Ru(OAc)2[(R)-binap Ru(OAc)2[(R)-tolbinap] Ru(OAc)2[(R)-xylbinap] 44-0153 44-0163 44-0164

Ru(OAc)2[(S)-binap Ru(OAc)2[(S)-tolbinap] Ru(OAc)2[(S)-xylbinap]

44-0152 Diacetato[(R)-(+)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] 250mg See page 31

ruthenium(II) Ru(OAc)2[(R)-binap] (325146-81-4) 44-0153 Diacetato[(S)-(-)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] 250mg See page 31

ruthenium(II) Ru(OAc)2[(S)-binap] (261948-85-0) 44-0162 Diacetato[(R)-(+)-2,2’-bis(di-p-tolylphosphino)-1,1’-binaphthyl] 250mg See page 31

ruthenium(II) Ru(OAc)2[(R)-tolbinap] (116128-29-1) 44-0163 Diacetato[(S)-(-)-2,2’-bis(di-p-tolylphosphino)-1,1’-binaphthyl] 250mg See page 32

ruthenium(II) Ru(OAc)2[(S)-tolbinap] (106681-15-6) 44-0164 Diacetato{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 32

binaphthyl}ruthenium(II) Ru(OAc)2[(R)-xylbinap] (374067-50-2) 44-0165 Diacetato{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 32 binaphthyl}ruthenium(II) Ru(OAc) [(S)-xylbinap] (374067-49-9) 2 Visit strem.com for new product announcements. 44 KITS - Takasago BINAP Ru Cymene Catalyst Kit

96-695196-6951 Takasago BINAP Ru Cymene Catalyst Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

Me Me Me Me Me Me Me Ph Me P Ph P Me P + - + - + - Ru Cl Ru Cl Ru Cl P Cl P Cl Me Cl Ph iPr P Ph Me iPr iPr

Me Me Me Me

44-0084 250mg 44-0088 250mg 44-0092 250mg [RuCl(p-cymene)((R)-binap)]Cl [RuCl(p-cymene)((R)-tolbinap)]Cl [RuCl(p-cymene)((R)-xylbinap}]Cl 44-0086 44-0089 44-0093 [RuCl(p-cymene)((S)-binap)]Cl [RuCl(p-cymene)((S)-tolbinap)]Cl [RuCl(p-cymene)((S)-xylbinap)]Cl

44-0084 Chloro[(R)-(+)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] 250mg See page 25 (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((R)-binap)]Cl (145926-28-9) 44-0086 Chloro[(S)-(-)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] 250mg See page 26 (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-binap)]Cl (130004-33-0) 44-0088 Chloro[(R)-(+)-2,2’-bis(di-p-tolylphosphino)-1,1’-binaphthyl] 250mg See page 27 (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((R)-tolbinap)]Cl (131614-43-2) 44-0089 Chloro[(S)-(-)-2,2’-bis(di-p-tolylphosphino)-1,1’-binaphthyl] 250mg See page 27 (p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-tolbinap)]Cl (228120-95-4) 44-0092 Chloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 28 binaphthyl}(p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((R)-xylbinap}]Cl (944451-24-5) 44-0093 Chloro{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 28 binaphthyl}(p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-xylbinap)]Cl (944451-25-6)

45 [email protected] . [email protected] . [email protected] . [email protected] KITS - Takasago BINAP Ru Diamine Catalyst Kit

96-695496-6954 Takasago BINAP Ru Diamine Catalyst Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

Me Me Me Me Me H H H iPr P P Cl N Me Cl H H Ru N OMe P OMe Ru H H Cl N Me N H H H P Me iPr Me Me OMe Me Me MeO 44-0212 250mg 44-0217 250mg

RuCl2[(R)-xylbinap][(R)-daipen] (R)-RUCY™-XylBINAP 44-0213 44-0218

RuCl2[(S)-xylbinap][(S)-daipen] (S)-RUCY™-XylBINAP

Me Me H H P Cl N Ph Ru P Cl N Ph H H Me Me 44-0224 250mg

RuCl2[(S)-xylbinap][(S,S)-dpen] 44-0226

RuCl2[(R)-xylbinap][(R,R)-dpen]

44-0212 Dichloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 33 binaphthyl}[(2R)-(-)-1,1-bis(4-methoxyphenyl)-3-methyl- 1,2-butanediamine]ruthenium(II)

RuCl2[(R)-xylbinap][(R)-daipen] (220114-32-9) 44-0213 Dichloro{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 34 binaphthyl}[(2S)-(+)-1,1-bis(4-methoxyphenyl)-3-methyl- 1,2-butanediamine]ruthenium(II)

RuCl2[(S)-xylbinap][(S)-daipen] (220114-01-2) 44-0217 Chloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’- 250mg See page 28 binaphthyl} [(2R)-(-)-1-(4-methoxyphenyl)- 1’-(4-methoxy phenyl-kC)-3- methyl-1,2-butanediamine]ruthenium(II) (R)-RUCY®XylBINAP (1384974-38-2) 44-0218 Chloro{(S)-(-)-2,2’-bis[di(3,5-xylyl) phosphino]-1,1’-binaphthyl} 250mg See page 28 [(2S)- (+)-1-(4-methoxyphenyl)-1’-(4-methoxyphenyl-kC)-3- methyl-1,2-butanediamine]ruthenium(II) (S)-RUCY®XylBINAP (1312713-89-5) 44-0224 Dichloro{(S)-(-)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl} 250mg See page 35 [(1S,2S)-(-)-1,2-diphenylethylenediamine]ruthenium(II)

RuCl2[(S)-xylbinap][(S,S)-dpen] (220114-03-4) 44-0226 Dichloro{(R)-(+)-2,2’-bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl} 250mg See page 34 [(1R,2R)-(+)-1,2-diphenylethylenediamine]ruthenium(II)

RuCl2[(R)-xylbinap][(R,R)-dpen] (220114-38-5)

Visit strem.com for new product announcements. 46 KITS - Takasago BINAP Ru Dimer Catalyst Kit

96-695296-6952 Takasago BINAP Ru Dimer Catalyst Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

-1 -1 o-tol o-tol Ph Ph Cl o-tol Ph Cl Cl Ph o-tol Cl P P P P Ru Cl Ru Ru Cl Ru P P P P Cl Cl Ph Cl Cl Ph o-tol Ph Ph o-tol o-tol o-tol + + Me2NH2 Me2NH2 250mg 250mg

44-0510 [NH2Me2][{RuCl((R)-binap)}2(µ-Cl)3] 44-0512 [NH2Me2][{RuCl((R)-tolbinap)}2(µ-Cl)3]

44-0511 [NH2Me2][{RuCl((S)-binap)}2(µ-Cl)3] 44-0513 [NH2Me2][{RuCl((S)-tolbinap)}2(µ-Cl)3]

250mg

44-0514 [NH2Me2][{RuCl((R)-xylbinap)}2(µ-Cl)3]

44-0515 [NH2Me2][{RuCl((S)-xylbinap)}2(µ-Cl)3]

44-0510 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2’- 250mg See page 37 bis(diphenylphosphino)-1,1’-binaphthyl]diruthenate(II)

[NH2Me2][{RuCl((R)-binap)}2(µ-Cl)3] (199684-47-4) 44-0511 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2’- 250mg See page 37 bis(diphenylphosphino)-1,1’-binaphthyl]diruthenate(II)

[NH2Me2][{RuCl((S)-binap)}2(µ-Cl)3] (199541-17-8) 44-0512 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-2,2’- 250mg See page 38 bis(di-p-tolylphosphino)-1,1’-binaphthyl]diruthenate(II)

[NH2Me2][{RuCl((R)-tolbinap)}2(µ-Cl)3] (749935-02-2) 44-0513 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-2,2’- 250mg See page 38 bis(di-p-tolylphosphino)-1,1’-binaphthyl]diruthenate(II)

[NH2Me2][{RuCl((S)-tolbinap)}2(µ-Cl)3] (309735-86-2) 44-0514 Dimethylammonium dichlorotri(µ-chloro)bis{(R)-(+)-2,2’- 250mg See page 36 bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}diruthenate(II)

[NH2Me2][{RuCl((R)-xylbinap)}2(µ-Cl)3] (944451-08-5) 44-0515 Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-2,2’- 250mg See page 36 bis[di(3,5-xylyl)phosphino]-1,1’-binaphthyl}diruthenate(II) [NH Me ][{RuCl((S)-xylbinap)} (µ-Cl) ] (944451-10-9) 2 2 2 3

47 [email protected] . [email protected] . [email protected] . [email protected] KITS - Takasago SEGPHOS® Ligand Kit

96-690096-6900 Takasago SEGPHOS® Ligand Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

t-Bu Me OMe O O O P Me P t-Bu 2 O O O PPh2 2 O O P t-Bu O PPh2 P Me O O OMe O Me t-Bu 2 2 250mg 250mg 250mg 15-0066 (R)-(-)-DTBM-SEGPHOS® 15-0136 (R)-(+)-SEGPHOS® 15-0478 (R)-(+)-DM-SEGPHOS® 15-0067 (S)-(+)-DTBM-SEGPHOS® 15-0137 (S)-(-)-SEGPHOS® 15-0479 (S)-(-)-DM-SEGPHOS®

15-0066 (R)-(-)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl) 250mg See page 1 phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% (R)-(-)-DTBM-SEGPHOS® (566940-03-2) 15-0067 (S)-(+)-5,5’-Bis[di(3,5-di-t-butyl-4-methoxyphenyl) 250mg See page 4 phosphino]-4,4’-bi-1,3-benzodioxole, min. 98% (S)-(+)-DTBM-SEGPHOS® (210169-40-7) 15-0136 (R)-(+)-5,5’-Bis(diphenylphosphino)-4,4’-bi-1,3- 250mg See page 4 benzodioxole, min. 98% (R)-(+)-SEGPHOS® (244261-66-3) 15-0137 (S)-(-)-5,5’-Bis(diphenylphosphino)-4,4’-bi-1,3- 250mg See page 5 benzodioxole, min. 98% (S)-(-)-SEGPHOS® (210169-54-3) 15-0478 (R)-(+)-5,5’-Bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 15 benzodioxole, min. 98% (R)-(+)-DM-SEGPHOS® (850253-53-1) 15-0479 (S)-(-)-5,5’-Bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 17 benzodioxole, min. 98% (S)-(-)-DM-SEGPHOS® (210169-57-6)

Visit strem.com for new product announcements. 48 KITS - Takasago SEGPHOS® Ru Catalyst Kit

96-690196-6901 Takasago SEGPHOS® Ru Catalyst Kit Sold in collaboration with Takasago. Components also available for individual sale. Contains the following:

MeO Me Me tBu Me tBu tBu O O OMe Me Me O Ph P Me P tBu Ph O Me O O + + P + Cl- - Ru Cl- Ru Ru Cl Cl O Cl P Cl O Me P tBu iPr O Ph iPr P iPr Ph O O OMe Me tBu tBu O tBu Me Me MeO 44-0096 250mg 44-0098 250mg 44-0102 250mg [RuCl(p-cymene)((R)-s egphos®)Cl [RuCl(p-cymene)((R)-dm-segphos®)Cl [RuCl(p-cymene)((R)-dtbm-segphos®)]Cl 44-0097 44-0099 44-0103 [RuCl(p-cymene)((S)-segphos®)Cl [RuCl(p-cymene)((S)-dm-segphos®)Cl [RuCl(p-cymene)((S)-dtbm-segphos®)]Cl

Me Me OMe Me tBu tBu O O tBu Me Me OMe Ph O Me Ph O O O O P Me tBu O P O O O P O Ru Ru Ru O O O P O P O O tBu Ph O P MeO O Ph O Me Me OMe Me O tBu O Me tBu tBu Me Me OMe 44-0168 250mg 44-0174 250mg 44-0180 250mg

Ru(OAc)2[(R)-segphos®] Ru(OAc)2[(R)-dm-segphos®] Ru(OAc)2[(R)-dtbm-segphos®] 44-0169 44-0176 44-0181 Ru(OAc) [(S)-segphos®] Ru(OAc) [(S)-dm-segphos®] Ru(OAc) [(S)-dtbm-segphos®] 2 2 2

Me Me Me Me Me Me O O H H H H Me H Me O P Cl N iPr O P Cl N Ph Ru OMe Ru O O P MeCl N P MeCl N Ph H H H H O O Me Me Me Me Me OMe Me 44-0214 250mg 44-0228 250mg

RuCl2[(R)-dm-segphos®][(R)-daipen] RuCl2[(R)-dm-segphos®][(R,R)-dpen] 44-0215 44-0229

RuCl2[(S)-dm-segphos®][(S)-daipen] RuCl2[(S)-dm-segphos®][(S,S)-dpen]

-1 -1 O O O O Xyl Xyl Ph Ph Ph Cl Cl Ph Xyl Cl Cl Xyl O P P O O P P O Ru Cl Ru Ru Cl Ru P P P P O Ph Ph O O Cl Cl Xyl O Ph Cl Cl Ph Xyl Xyl Xyl O O O + O + Me2NH2 Me2NH2

44-0518 250mg 44-0520 250mg

[NH2Me2][{RuCl((R)-segphos®)}2(µ-Cl)3] [NH2Me2][{RuCl((R)-dm-segphos®)}2(µ-Cl)3] 44-0519 44-0521

[NH2Me2][{RuCl((S)-segphos®)}2(µ-Cl)3] [NH2Me2][{RuCl((S)-dm-segphos®)}2(µ-Cl)3]

49 [email protected] . [email protected] . [email protected] . [email protected] KITS - Takasago SEGPHOS® Ru Catalyst Kit 44-0096 Chloro[(R)-(+)-5,5’-bis(diphenylphosphino)-4,4’-bi-1,3- 250mg See page 25 benzodioxole](p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((R)-segphos®)]Cl (944451-28-9) 44-0097 Chloro[(S)-(-)-5,5’-bis(diphenylphosphino)-4,4’-bi-1,3-ben- 250mg See page 25 zodioxole](p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-segphos®)]Cl (944451-29-0) 44-0098 Chloro{(R)-(+)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 27 benzodioxole}(p-cymene)ruthenium(II) chloride [RuCl(p- cymene)((R)-dm-segphos®)]Cl (944451-30-3) 44-0099 Chloro{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 27 benzodioxole}(p-cymene)ruthenium(II) chloride [RuCl(p- cymene)((S)-dm-segphos®)]Cl (944451-31-4) 44-0102 Chloro{(R)-(-)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphenyl) 250mg See page 24 phosphino]-4,4’-bi-1,3-benzodioxole}(p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((R)-dtbm-segphos®)]Cl (944451-32-5) 44-0103 Chloro{(S)-(+)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphenyl) 250mg See page 24 phosphino]-4,4’-bi-1,3-benzodioxole}(p-cymene)ruthenium(II) chloride [RuCl(p-cymene)((S)-dtbm-segphos®)]Cl (944451-33-6) 44-0168 Diacetato[(R)-(+)-5,5’-bis(diphenylphosphino)-4,4’-bi-1,3- 250mg See page 30

benzodioxole]ruthenium(II) Ru(OAc)2[(R)-segphos®] (944450-48-0) 44-0169 Diacetato[(S)-(-)-5,5’-bis(diphenylphosphino)-4,4’-bi-1,3- 250mg See page 30

benzodioxole]ruthenium(II) Ru(OAc)2[(S)-segphos®] (373650-12-5) 44-0174 Diacetato{(R)-(+)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 32

benzodioxole}ruthenium(II) Ru(OAc)2[(R)-dm-segphos®] (944450-49-1) 44-0176 Diacetato{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 32

benzodioxole}ruthenium(II) Ru(OAc)2[(S)-dm-segphos®] (944450-50-4) 44-0180 Diacetato{(R)-(-)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphe- 250mg See page 30 nyl)phosphino]-4,4’-bi-1,3-benzodioxole}ruthenium(II)

Ru(OAc)2[(R)-dtbm-segphos®] (1025477-38-6) 44-0181 Diacetato{(S)-(+)-5,5’-bis[di(3,5-di-t-butyl-4-methoxyphe- 250mg See page 30 nyl)phosphino]-4,4’-bi-1,3-benzodioxole}ruthenium(II)

Ru(OAc)2[(S)-dtbm-segphos®] (1025476-84-9) 44-0214 Dichloro{(R)-(+)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 33 benzodioxole}[(2R)-(-)-1,1-bis(4-methoxyphenyl)-3-methyl-

1,2-butanediamine]ruthenium(II) RuCl2[(R)-dm-segphos®] [(R)-daipen] (944450-43-5) 44-0215 Dichloro{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 33 benzodioxole}[(2S)-(+)-1,1-bis(4-methoxyphenyl)-3-methyl-

1,2-butanediamine]ruthenium(II) RuCl2[(S)-dm-segphos®] [(S)-daipen] (944450-44-6) 44-0228 Dichloro{(R)-(+)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 33 benzodioxole}[(1R,2R)-(+)-1,2-diphenylethylenediamine]

ruthenium(II) RuCl2[(R)-dm-segphos®][(R,R)-dpen] (944450-45-7) 44-0229 Dichloro{(S)-(-)-5,5’-bis[di(3,5-xylyl)phosphino]-4,4’-bi-1,3- 250mg See page 33 benzodioxole}[(1S,2S)-(-)-1,2-diphenylethylenediamine]

ruthenium(II) RuCl2[(S)-dm-segphos®][(S,S)-dpen] (944450-46-8) 44-0518 Dimethylammonium dichlorotri(µ-chloro)bis[(R)-(+)-5,5’- 250mg See page 36 bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole]diruthenate(II)

[NH2Me2][{RuCl((R)-segphos®)}2(µ-Cl)3] (346457-41-8) 44-0519 Dimethylammonium dichlorotri(µ-chloro)bis[(S)-(-)-5,5’- 250mg See page 37 bis(diphenylphosphino)-4,4’-bi-1,3-benzodioxole]diruthenate(II)

[NH2Me2][{RuCl((S)-segphos®)}2(µ-Cl)3] (488809-34-3) 44-0520 Dimethylammonium dichlorotri(µ-chloro)bis{(R)-(+)-5,5’-bis[di(3,5- 250mg See page 35

xylyl)phosphino]-4,4’-bi-1,3-benzodioxole}diruthenate(II) [NH2Me2] [{RuCl((R)-dm-segphos®)}2(µ-Cl)3] (935449-46-0) 44-0521 Dimethylammonium dichlorotri(µ-chloro)bis{(S)-(-)-5,5’-bis[di(3,5- 250mg See page 36

xylyl)phosphino]-4,4’-bi-1,3-benzodioxole}diruthenate(II) [NH2Me2] [{RuCl((S)-dm-segphos®)}2(µ-Cl)3] (944451-14-3)

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