Organophosphorus Chemistry (Kanda, 2019)

Organophosphorus Chemistry (Kanda, 2019)

Baran lab Group Meeting Yuzuru Kanda Organophosphorus Chemistry 09/20/19 bonding and non-bonding MOs of PH3 bonding and non-bonding MOs of PH5 # of R P(III) ← → P(V) O P P R R R R R R phosphine phosphine oxide D3h C3v C2v O O JACS. 1972, 3047. P P P P R NH R OH R OH R NH Chem. Rev. 1994, 1339. R 2 R R R 2 D C phosphineamine phosphinite phosphinate phosphinamide 3h 4v O O O R P R P R P R P R P R P NH2 NH2 OH OH NH2 NH2 H2N HO HO HO HO H2N phosphinediamine phosphonamidite phosphonite phosphonate phosphonamidate phosphonamide O O O O H N P P P P P P P P 2 NH HO HO HO HO HO HO H2N H N 2 NH2 NH2 OH OH NH2 NH2 NH2 2 H2N HO HO HO HO H2N H2N phosphinetriamine phosphorodiamidite phosphoramidite phosphite phosphate phosphoramidate phosphorodiamidate phosphoramide more N O more O Useful Resources more N P P P Corbridge, D. E. C. Phosphorus: Chemistry, Biochemistry and H OH H H H H H H H Technology, 6th ed.; CRC Press Majoral, J. P. New Aspects In Phosphorus Chemistry III.; Springer phosphinous phosphane phosphane Murphy, P. J. Organophosphorus Reagents.; Oxford acid oxide Hartley, F. R. The chemistry of organophosphorus compounds, O O volume 1-3.; Wiley P P P Cadogan. J. I. G. Organophosphorus Reagents in Organic H OH H OH H OH HO HO H Synthesis.; Academic Pr phosphonate phosphonus acid phosphinate Not Going to Cover ↔ (phosphite) Related GMs Metal complexes, FLP, OPV Highlights in Peptide and Protein NH S R • oxidation state +5, +4, +3, +2, +1, 0, -1, -2, -3 Synthesis (Malins, 2016) R P-Stereogenic Compounds P P R P • traditionally both +3 and -3 are written as (III) R • 13/25th most abundant element on the earth (Rosen, 2014) R • but extremely rare outside of our solar system Ligands in Transition Metal phosphine imide phosphine sulfide phosphorane Catalysis (Farmer, 2016) Baran lab Group Meeting Yuzuru Kanda Organophosphorus Chemistry 09/20/19 Me P Me Me Low-Coordinate Low Oxidation State P tBu tBu P P phosphaalkyne R N P PivCl 2 P Me Cl TMS OTMS NaOH R = tBu Nb N tBu PTMS3 P O H O P NR2 then Na/Hg tBu N -2 Nb tBu R2N Me Nb N tBu 5x10 mbar, 160 ºC NR2 95% R2N Me N O 1. Tf2O Me Nb 2. Δ tBu R2N O 1. LAH NR2 2. DBU R = Me R2N P recyclable Me EtO HP P R EtO J. Chem. Soc. Chem. JACS. 2000, 13916. Commun. 1992, 415. PPh3 20-80 ºC PPh3 Cl JACS. 2012, 134, 13978. P R P 1. Me2NPCl2 Mg 2. HCl JACS. 2014, 13586. R JACS. 2018, 17985.: P31 nuclear spin- rotation coupling (J = 0←1) (R = Me) R ≠ H, tBu tBu O N R’ tBu Ph O N R' Ph N O Ph Ph R X N P P R N PhMe, tBu P V tBu P [2+1] then O Cl Cl P O 100 ºC, 14 days X 1,3-X shift Cl P P tBu N Ph R R P R Ts tBu tBu P A B C Ts N N P P A C R 2TsN3 P P B [2+3] P N N N Δ or Zr cat R P P N tBu P tBu P R R P tBu P tBu N O N R Ts Ts H O ACIE. 1984, 900. P ene Weidner. S (2002) PhD thesis, University of Kaiserslautern R P R Chem. Rev. 1990, 191. Chem. Rev. 1990, 191. JACS. 1982, 4484. ACIE. 1987, 1257. ACIE 1989, Et3N Et3N LnM R ML [2+2] 225. Phosphorus Sulfur. 1987, 479. Bull. Soc. Chem. Br Br P P P n THF, -5 ºC Br THF, 40 ºC Fr. 1995, 652. Synthesis. 1998, 125. ACIE. 1986, Br Br P Br M = Co, Rh, Hf, Zr 644. ACIE, 1988. 1157. Chem. Ber. 1988, 637. ACIE. P TL. 1989 817. R Br Br 1995, 2227. ACIE. 1998, 1233. Chem. Eur. J. 2000, Polyhedron. 1990, 991 4558. ACIE. 1989, 1013. ACIE. 1992, 758. Baran lab Group Meeting Yuzuru Kanda Organophosphorus Chemistry 09/20/19 Phosphide Anion C, SiO2 1200-1400 ºC • reduction of energy inputs O O Cl2 O • less waste O HSiCl3 (neat) versatile 1 Mt/y O P P O • no elemental P P P organophosphorus O O 110 ºC, 72 h Cl Si SiCl • no Cl2 oxidation P O O 3 3 precursor 65%, gram scale O O •3TBA•2H2O O O Ph O 1. [TBA]3[P3O9]•2H2O, P Cl HSiCl , 64% (one-pot) P N 3 H Cy O O O H2SO4 HO 2. H O 2 2 HO2C Ph Ph Me Me Me 90 Mt/y fosinopril Direct Method original prep: 4-phenyl-1-butene, H3PO2, AIBN, 93% contaminated w/ 2% anti-Markovnikov regioisomer H3PO4, TBACl Oct Cl Oct PH2 JACS. 2019, 6375. OPRD. 1997, 315. Science 2018, 1383. JACS. 2019, 6375. HSiCl3, 110 ºC P-P bonds for detail see; Corbridge, D. E. C. Phosphorus: Chemistry, Low-Coordinate Hypervalent Phosphorus useful reviews Biochemistry and Technology, 6th ed.; CRC Press JACS. 1987, 627. Chem. Rev. 1994, 1215. TIPS P tBu tBu tBu tBu O O O O tBu Nb XH N N tBu X if X = OR N TIPS -2 tBu Ar Ar N P N P N P N P Phospha-Wittig P PMo(N[tBu]Ar) TIPS H O Ar 3 OR P P P O O reductive O O P tBu TIPS elimination tBu N Mo tBu tBu tBu tBu Mo tBu N tBu if X = H stable if N tBu N tBu N Ar JACS. 2009, 8764. X = H, NHR N Ar 10-P-3 ADPO R Ar Ar Ar N P • T-shaped O Ar O O hν P Me • strongly reducing N P iPrOH P OiPr P P P • formally dianionic P O O N P Me tBu P P hex, DMSO tBu • pseudo-TBP H P 15% (34% brsm) 8-P-3 8-P-3 Me Me Me O Me ACIE. 2010, 7516. w/o unsaturation JACS. 2014, 13586. 10-P3 not observed R stable Cl 1. AlCl P 3 2. LAH P Δ OH O O P P(OMe)3 H BH3•DMS 55% For P2 surrogate also see; NH N P N P Science 2006, 1276. OMe instead BH adduct recall: phosphaalkyne precursor 3 Inorg. Chem. 2007, 7387. OH O dimer was isolated - O P3 ; ACIE. 2010, 1595. Baran lab Group Meeting Yuzuru Kanda Organophosphorus Chemistry 09/20/19 R = H active reductant tBu stepwise tBu R = Pr, O oxidative Naph Naph R R O= 2,6-diiPrC6H3 N N addition N N P NH R R H P 2 N H Me H Me ADPO N P N N R Me Me H H N P first-order w/ H no H cat. 1 mol%, HBpin ADPO, [NH R]3 O RH2N reductive N N 2 O H tBu elimination 91% JACS. 2019, 14083. tBu Ar N Br 91:1 er N Br also see; JACS. 2018, 652. tBu tBu tBu N H O O Ar Phosphine Me Ph P P H H N NH NH2 miscellaneous phosphine synthesis; for more info see GM by Rosen (2014) NH Bn N 3 N 2 N Ar P P tBu Ar N P N P P R R H Me H rt N 3RX P tBu tBu Ar P P N N Ar Ti tBu benzene, rt R O NH2iPr O Ar = 2,6-diiPrC H P 6 3 tBu N 64-97% tBu tBu JACS. 2014, 4640. tBu 3,5-Me2C6H3 New J. Chem., 2010, 1533. other oxidative addition reactivities of ADPO JACS. 2014, 16764 R = Ph, Cy, TMS, Ph3Sn Org. Chem. Front. 2018, 3421. tBu Ph Cl 1. Et N O O O Cl O N P 3 P F 2. H O CO Et Cl O O O Br 2 2 F F C P N CO Et N P CF O 3 H 2 3 F C Ph 3. HSCH2CH2SH, S F 3 tBu Br O Cl F C O BF3•Et2O tBu P O 3 S O O O 4. Raney-Ni tBu O O 5. LAH tBu F O F N P 6. HCl NaOH F3C CF3 Ph w/ F CF3 w/ o-chloranil w/ Heteroat. Chem. 1993, 213. JACS. 1987, 627. JACS. 1987, 627. P P CF3 tBu Na spiro conjugation O N P O CF3 Tet. 1983, 4225. O CF 3 N P CN F C CF3 N P 3 H [2+3] CF3 Ph chemische berichte, CF3 CF3 N2 CF3 tBu CF Ph NaOMe 1966, 514. CF O 3 Ar P F C CF Δ O 3 Ph w/ 3 3 tBu P P tBu Ph CN JACS. 1987, 627. D symmetric orbitals Ph 2d π Ph NO2 NO JACS. 1967, 5208. S ≈ 20% of planar system 2 Phosphenium Cation; Chem. Rev. 1985, 367. styrene (10 eq), via tBu Me4NF (15 mol%), tBu P(CH OH) P Ph 2 3 [FpTHF][BF4] (10 mol%) P N P N P N tBu Fe CO BF 73%, >99:1 dr F 4 CH O BF4 CO Ph 2 Me Me ACIE. 1964, 384. Me JACS. 2019, 13336. Baran lab Group Meeting Yuzuru Kanda Organophosphorus Chemistry 09/20/19 Me Me Me Me 1. PhCCCO Me NHCbz 2 NHCbz Ph3P, Ph3P•HClO4 NHCbz Me Me 2. S PPh3 PhPX2 Δ 8 R Ar R CO2H 5 mA, DCM, -30 ºC R CHO P P O (+)graphite/(-)graphite TL.

View Full Text

Details

  • File Type
    pdf
  • Upload Time
    -
  • Content Languages
    English
  • Upload User
    Anonymous/Not logged-in
  • File Pages
    13 Page
  • File Size
    -

Download

Channel Download Status
Express Download Enable

Copyright

We respect the copyrights and intellectual property rights of all users. All uploaded documents are either original works of the uploader or authorized works of the rightful owners.

  • Not to be reproduced or distributed without explicit permission.
  • Not used for commercial purposes outside of approved use cases.
  • Not used to infringe on the rights of the original creators.
  • If you believe any content infringes your copyright, please contact us immediately.

Support

For help with questions, suggestions, or problems, please contact us