DOCSLIB.ORG

Umicore CX Catalysts Palladium Catalyzed Cross-Coupling Reactions 2 3

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Umicore CX Catalysts Palladium Catalyzed Cross-Coupling Reactions 2 3 Umicore CX Catalysts Palladium catalyzed cross-coupling reactions 2 3 Specific, well-defined precatalysts and ready-made catalysts UMICORE PMC WILL ASSIST YOU WITH OUR EXPERTISE IN ACTIVITY EXACTLY AS FAR AS IT IS NEEDED TO MEET YOUR NEEDS Palladium catalyzed C-C- and C-X bond forming reactions have undergone remarkable developments in the last 25 years [1]. Numerous research groups, inspired by the 2010 Chemistry Nobel Prize awardees Heck, Negishi and Suzuki [2], have developed new palladium precursors, ligands and catalysts to fully utilize this versatile, synthetic tool in organic chemistry. Some of these palladium complexes have transitioned into a broad range of applications spanning from synthesis of agrochemicals, use in natural products and active pharmaceutical ingredients down to appearing in materials for electronic applications. Umicore CX catalysts at glance: • Alternative Palladium precursors • Well-defined, ready-to-use Palladium phosphine complexes • Selective & active Palladium N-heterocyclic carbene complexes • Efficient Palladium recovery streams [1] a) Handbook of Organopalladium Chemistry for Organic Synthesis, (Eds.: E. Negishi, F. Diederich) Wiley-VCH, 2002, b) Metal-Catalyzed Cross Coupling Reactions, (Eds.: A. de Meijere, F. Diederich) Wiley-VCH, 2004, c) Angew. Chem. Int. Ed. 2012, 51, 5062 [2] http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2010/popular-chemistryprize2010.pdf 4 5 CROSS-COUPLING REACTIONS ARE A TRANSITION METAL CATALYZED COUPLING OF AN ORGANIC ELECTROPHILE (I.E. ORGANIC HALIDE) WITH AN ORGANIC NUCLEOPHILE. SEVERAL NAME REACTIONS HAVE BEEN DEVELOPED USING ORGANOMETALLIC CARBON NUCLEOPHILES HALOGEN BONDS. Kumada Sonogashira-Hagihara Stille Mizoroki-Heck Carbonylation Buchwald - Hartwig -Amination Cyanation Suzuki -Miyaura Negishi Hiyama In addition to conventional product offerings Regardless of whether you need to perform a such as the palladium precursors and highly Suzuki coupling with strongly hindered and/or active phosphine catalysts, Umicore has deactivated substrates or a Negishi coupling developed a number of stable, user-friendly, with substrates carrying sensitive functional well-defined and powerful Palladium(0) and groups, or you are searching for a catalyst for LEGEND Palladium(II) N-heterocyclic carbene (NHC) a Buchwald-Hartwig Amination reaction, we catalysts that are commercially available at will provide you with the appropriate catalytic X = I, Br, Cl, or OTf industrial scale. active complex. 6 7 Examples Buchwald-Hartwig amination reaction(3) Mizoroki-Heck Coupling(6) OMe OMe 5 mol% [Pd(dppf)Cl2] 1.2 eq.NaOtBu + N THF, 3 h, 100 °C N substrate 1: substrate 2 2:1 substrate 1: substrate 2 1:1 I H2N O H 5 mol% Pd(OAc)2 2.5 mol% Pd2dba3 t 1 N 1.2 eq. 96% yield 5 mol% HBF4*P Bu3 5 mol% XPhos t 1.5 eq. K2CO3 3 eq. NaO Bu N + toluene, 110 °C toluene, mW N O 45 min, 110 °C O Br O O 89% yield 79% yield 5 mol% [Pd(dppf)Cl2] 2 1.2 eq. NaOtBu + H2N THF, 3 h, 100 °C Br N H 1.2 eq. 96% yield NC (7) NC 5 mol% [Pd(dppf)Cl2] Negishi Coupling 1.2 eq. NaOtBu + H2N THF, 3 h, 100 °C N Br H CN CN O 1.2 eq. 93% yield t Cl 2 mol% [Pd(P Bu3)2] + ClZn NMP/THF 18 h, 100 °C O O O O 1.5 eq. 76% yield t s (4) Cl 2 mol% [Pd(P Bu3)2] Bu + ClZn sBu Palladium catalyzed decarboxylation NMP/THF 24 h, 100 °C t 5 mol% Pd[P( Bu3)]2 H 1.5 eq. 70% yield 1 eq. TBACl N N O 1.5 eq. Cs2CO3 N Ph + PhBr + DMF, µW, Ph OH 8 min, 170 °C Ph 2 eq. 74% yield trace Newman-Kwartz rearrangement(8) O NMe2 S NMe2 t 2 mol% [Pd(P Bu3)2] S toluene, 4 h, 100 °C O Palladium catalyzed oxidative coupling(5) F3C F3C > 99% yield OH 5 mol% Umicore CX21 OH t 2.2 eq.KO Bu O NMe S NMe + 2 t 2 toluene, 1.5 h, 80 °C 2 mol% [Pd(P Bu3)2] Cl S toluene, 4 h, 100 °C O 2.1 eq. 92% yield > 99% yield [3] J. Am. Chem. Soc. 1996, 118, 7217 [6] J. Am. Chem. Soc. 2008, 130, 3266 [4] J. Am. Chem. Soc. 2006, 128, 11350 [7] J. Am. Chem. Soc. 2001, 123, 2719 [5] J. Org. Chem. 2011, 76, 1390 [8] Angew. Chem. Int. Ed. 2009, 48, 7612 8 9 Suzuki-Miyaura Coupling(9,10) First Class Palladium metal 50 ppm Umicore CX21 N Cl t 1.1 eq. KO Bu N + (HO)2 B tech. grade IPA 3 h, 80 °C recycling technology 1.05 eq. 92% yield UMICORE’S PRECIOUS METAL RECYCLING CAPABILITIES CAN GIVE 1 mol% Umicore CX32 (HO)2B 1.1 eq. KOtBu MORE VALUE TO YOUR PROCESS. THE SOONER THE BETTER! + Br tech. grade IPA 1.5 h, rt 1.05 eq. 92% yield Planning to associate a metal recycling loop to your industrial scale Palladium catalyzed cross-coupling re- action will bring significant additional cost effective- Cl 50 ppm Umicore CX21 1.1 eq. KOt Bu ness to your process. The earlier we speak, the better + (HO)2B tech. grade IPA we can adjust the separation and recycling processes 3 h, 80 °C to offer you maximized precious metal savings. Con- 1.05 eq. 92% yield tact us to discover the accuracy and efficiency of our Palladium recycling technologies and their impact on the economics of your chemical synthesis. Palladium catalyzed oxidative carbonylation(11) [Pd]/ligand O H 0.5 eq. TBP + OH + CO 16 h, 120 °C O Umicore PMC cross-couplings 15 eq. 10 atm 81% yield with 5 mol% PdCl2 and 5 mol% Xantphos 80% yield with 2 mol% Pd(Xantphos)Cl2 precatalysts and ready-to-use catalysts ADVANTAGES READY TO USE EMPIRICAL FORMULA CHEMICAL NAME CAS-No PRODUCT-No VERSUS IN SITU FORMED CATALYSTS: +2 Palladium(II) chloride 7647-10-1 3000036292 PdCl2 • higher reactivity +2 • consistent reactivity profile for optimum reactivity control Diacetylacetonatopalladium(II) 14024-61-4 3000034510 [Pd(acac)2] • no catalytically inactive palladium-ligand species +2 Bis(acetonitrile)dichloropalladium(II) 14592-56-4 3000036037 • higher subsequent end-product purity level [Pd(CH3CN)2Cl2] +2 • no impurities from palladium precursor and no ligand by Bis(benzonitrile)dichloropalladium(II) 14220-64-5 3000036142 incomplete in situ transformation [Pd(C6H5CN)2Cl2] +2 • efficient utilization of stable, pure & active catalyst with Dichloro(1,5-cyclooctadiene)palladium(II) 12107-56-1 3000034509 correct stoichiometry [Pd(cod)Cl2] +2 • no loss of palladium and ligand by incomplete in situ Palladium(II) acetate 3375-31-3 3000034514 transformation or ligand decomposition [Pd(OAc)2]3 +2 • no in situ catalyst preformation step Palladium(II) pivalate 106224-36-6 3000020655 [Pd(OOCtBu) ] • Easy catalyst operation for improved 2 3 process safety & simplicity +2 Bis(η3-allyl)di(μ-chloro)dipalladium(II) 12012-95-2 3000034516 [Pd(allyl)Cl]2 +2 Di(μ-chloro)bis(η3-cinnamyl)dipalladium(II) 12131-44-1 3000034515 [Pd(cinnamyl)Cl]2 0 Tris(dibenzylideneacetone)dipalladium(0) 51364-51-3 3000034523 [9] [Pd (dba) ] x dba Chem. Eur. J. 2006, 12, 5142 2 3 [10] J. Am. Chem. Soc. 2006, 128, 4101 [11] J. Am. Chem. Soc. 2012, 134, 9902 10 11 READY TO USE PALLADIUM PHOSPHINE CATALYSTS PALLADIUM N-HETEROCYCLIC CARBENE CATALYSTS Palladium Vinylsiloxane TRADE NAME EMPIRICAL FORMULA CAS-No PRODUCT-No TRADE NAME EMPIRICAL FORMULA CAS-No PRODUCT-No Catalysts 0 Si Si O Umicore CX11 NHC = IPr 649736-75-4 3000034519 Si Si [(IPr)Pd(NQ)] O 0 O 2 O Pd Pd O Umicore CX61 252062-59-2 3000036051 Pd(vs)c NHC Pd Pd NHC Si Si O 0 Umicore CX12 NHC = IMes 467220-49-1 3000034521 O [(IMes)Pd(NQ)]2 iPr i 0 P Pr US 6 316 380 and Umicore CX14 NHC = SIMes 955998-76-2 3000036042 Si WO 2004 014550 apply. [(SIMes)Pd(NQ)]2 O Fe Pd 0 Si Umicore CX62 1708984-17-1 3000036052 +2 P [Pd(dippf)(vs)tol] Umicore CX21 NHC = IPr 478980-03-9 3000034520 iPr NHC [(IPr)Pd(allyl)CI] iPr Pd WO2015 059049 and foreign equivalents apply. +2 Umicore CX22 NHC = IMes 478980-04-0 3000034522 Cl [(IMes)Pd(allyl)CI] Palladium Monodentate TRADE NAME EMPIRICAL FORMULA CAS-No PRODUCT-No +2 Phosphine Catalysts US 6 316 380, WO 2004 014550 and Umicore CX23 NHC = SIPr 478980-01-7 3000034526 foreign equivalents apply. [(SIPr)Pd(allyl)CI] PPh 3 NHC +2 0 Pd PPh3 Umicore CX31 NHC = IPr 884879-23-6 3000034528 Pd-Tetrakis 14221-01-3 3000034517 Pd Ph3P [(IPr)Pd(cinnamyl)CI] [Pd(PPh3)4] Cl PPh3 +2 Umicore CX32 NHC = SIPr 884879-24-7 3000034527 [(SIPr)Pd(cinnamyl)CI] 0 P Pd P Fu catalyst 53199-31-8 3000034529 t US 6 316 380, WO 2004 014550 and +2 [Pd[P( Bu3)]2] Umicore CX33 NHC = IPr* 1380314-24-8 3000036301 foreign equivalents apply. [(IPr*)Pd(cinnamyl)CI] +2 Br NHC Cl Cl Umicore CX41 NHC = IPr 444910-17-2 3000034518 +1 [(IPr)PdCI ] tBu P Pd Pd PtBu Pd Pd 2 2 3 3 Umicore CX71 t 185812-86-6 3000036049 [PdBr[P( Bu3)]]2 Cl Cl NHC Br +2 US 6 316 380, WO 2004 014550 and Umicore CX42 NHC = SIPr 627878-09-5 3000034610 +2 foreign equivalents apply. [(SIPr)PdCI2]2 Umicore CX72 29934-17-6 3000034513 R1= PCy3 [Pd(PCy ) CI ] 3 2 2 NHC 0 Umicore CX51 NHC = IPr 478019-87-3 3000036038 +2 Pd [(IPr)Pd(vs)] R1= PPh3 Umicore CX73 13965-03-2 3000034512 [Pd(PPh3)2CI2] 0 Umicore CX52 NHC = IMes 441018-46-8 3000036039 +2 Si Si [(IMes)Pd(vs)] Cl R1 R1= P(o-tol)3 Umicore CX74 40691-33-6 3000034511 O Pd [Pd[P(o-tol)3]2CI2] R1 Cl US 6 316 380, WO 2004 014550 and 0 +2 Umicore CX54 NHC = SIMes 1004291-85-3 3000036043 foreign equivalents apply.
Load more

Recommended publications
  • Desperately Seeking for the Catalytic Species in Suzuki-Miyaura Reaction Amine Bourouina
    Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction Amine Bourouina To cite this version: Amine Bourouina. Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction. Chemical and Process Engineering. Université de Lyon, 2019. English. NNT : 2019LYSE1258. tel-02482607 HAL Id: tel-02482607 https://tel.archives-ouvertes.fr/tel-02482607 Submitted on 18 Feb 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. N°d’ordre NNT : 2019LYSE1258 THESE de DOCTORAT DE L’UNIVERSITE DE LYON opérée au sein de l’Université Claude Bernard Lyon 1 Ecole Doctorale ED206 Ecole Doctorale de Chimie de Lyon Spécialité de doctorat : Discipline : Procédés Soutenue publiquement le 28/11/2019, par : Amine BOUROUINA Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction Devant le jury composé de : FERRIGNO Rosaria, Professeure des Universités, Université Lyon Présidente HII King Kuok (Mimi), Professeure, L'Imperial College de Londres Rapporteuse RIANT Olivier, Professeur ordinaire, Université Catholique de Louvain Rapporteur
    [Show full text]
  • Novel Reagents and Catalysts for Facilitating Synthesis Peppsi™: A
    NOVELPEppSI ™REAGE: A NENWTS GE ANNERATIOD CATALYSTSN OF AIR FOR-STA FABCLEILITATI Pd PNRECG SATALYSTSYNTHESIS VOL. 39,38, NO.NO.1 4 •• 20062005 ROM Polymerization in Facilitated Synthesis Pd–N-Heterocyclic CarbenePolyurea-Encapsulated (NHC) Catalysts for Cross-CouplingPalladium ReactionsCatalysts sigma-aldrich.com New Products from Aldrich R&D BD3–THF Solution Stabilized with NIMBA and Alkynylboronates Me-CBS Solutions in THF Alkynylboronates participate in a variety of regio- and stereoselective The asymmetric borane reduction of prochiral ketones catalyzed by (R)- carbon–carbon bond-forming reactions including enyne cross metathesis 1 2 3 or (S)-Me-CBS provides a facile method for accessing chiral secondary (CM), Alder-ene, and Dötz annulation reactions. Products obtained alcohols.1 We are pleased to introduce N-isopropyl-N-methyl-tert-butylamine from these reactions are either alkenyl or arylboronates, which are active coupling partners in (NIMBA) stabilized BD3–THF solutions for the preparation of isotopically 2 Suzuki and Heck CH3 labeled alcohols. Amine-stabilized borane–THF solutions exhibit enhanced BPin O CH3 shelf-life over those containing other stabilizers, and additionally, higher reactions. BPin = B R 3 O CH3 levels of enantiomeric excess are obtained. Deuterium-labeled alcohols CH3 may also be synthesized through (1) Kim, M.; Lee, D. O HO D the sequence of hydroboration– OBD3 Org. Lett. 2005, 7, CH3 CH3 1865. (2) (a) Hansen, R' R' Cr(CO) oxidation of olefins. Either method (R)-Me-CBS 5 R R E. C.; Lee, D. J. Am. H3CO [Ru]+ of alcohol preparation gives high Chem. Soc. 2005, 127, [Ru] levels of deuterium incorporation R Yield (%) ee (%)D atom % 3252.
    [Show full text]
  • Functionalized Nitrogen Ligands (CN) for Palladium Catalyzed Cross
    Journal of Organometallic Chemistry 881 (2019) 79e129 Contents lists available at ScienceDirect Journal of Organometallic Chemistry journal homepage: www.elsevier.com/locate/jorganchem Review Functionalized nitrogen ligands (CeN) for palladium catalyzed cross- coupling reactions (part II) Arjun Kumbhar Department of Chemistry, Padmabhushan Dr. Vasantraodada Patil College, Tasgaon, Affiliated to Shivaji University, Kolhapur, Maharashtra, 416312, India article info abstract Article history: In recent years, considerable effort has been focused in Pd catalyzed cross-coupling reactions, especially Received 6 April 2018 the use of less reactive and economically viable substrates like aryl chlorides. Unfortunately, Pd com- Received in revised form plexes containing the ligands having only N as a donor atom has some limitations, as it couples, mostly 22 September 2018 aryl iodides and bromides with different nucleophiles, and shows less activity towards aryl chlorides. Accepted 24 September 2018 This restriction can overwhelm by the use of Pd complexes containing N in combination with the C as a Available online 3 October 2018 donor atom such as palladacycles, pincers, PEPPSI and carbene ligands. The advantages of these ligands include high activity with enhanced selectivity, less toxicity, moisture, air as well as thermal stability. Keywords: Palladium Most importantly, such complexes have broad applications in catalysis under ambient conditions. This e Nitrogen ligands part of compressive review highlights the results of the highly active C N based Pd complexes and their NeC complexes applications in cross-coupling reactions. In the next part, we will cover all ligands and complexes con- Cross-couplings taining N in combination with P, O and S as a donor atoms (Pd catalysts based on CeP, CeO and CeS ligands).
    [Show full text]
  • Investigation of PEPPSI Precatalysts for Controlled Polymerization of Π-Conjugated Polymers from Cheap Starting Materials
    Investigation of PEPPSI precatalysts for controlled polymerization of π-conjugated polymers from cheap starting materials Thesis submitted in partial fulfilment of the requirement for a degree of Doctor of Philosophy at the University of London Benjamin John Groombridge Page | 1 Acknowledgements I would firstly like to thank my supervisors, Dr. Igor Larrosa and Dr. Stephen M. Goldup, for giving me the opportunity to carry out the research described in this thesis. Special gratitude to both of you, for the invaluable expert guidance and support during my PhD. I would like to thank the following people for the words of wisdom and practical input during the course of my PhD: Prof. Mike Watkinson, Dr. Chris Bray, Dr. Joby Winn, Dr. Jamie Lewis, Dr. Catherine Fletcher, Dr. Saidul Islam, Dr. Xacobe Couso Cambeiro, Dr. Nanna Ahlsten, Dr. Paolo Ricci, Dr. Carlos Arróniz, Dr. Sara Preciado, Dr. Francisco Juliá-Hernández, Dr. Josep Cornella, Dr. Tanya Boorman, Dr. Saidul Islam, Robert Bordoli, Ed Neal, Jessica Pancholi, Katrina Krämer, Rachel Grainger, Marco Simonetti, Junfei Luo, Adam Johnston, Gregory Perry and Nicky Willis. The research described would not have been possible without the fantastic support from both NMR and analytic services in particular Dr. Harold Toms and Dr. Ian Sanders. Finally, I would like to thank my friends and family for their support and advice throughout my PhD and during the writing up period. Page | 2 Declaration I declare that the scientific work presented in this thesis is my own and was carried out in the School of Biological and Chemical Science at Queen Mary, University of London between September 2010 and September 2014.
    [Show full text]
  • APPLICATION of Pd-NHC COMPLEXES in CHALLENGING
    APPLICATION OF Pd-NHC COMPLEXES IN CHALLENGING AMINATION REACTIONS SEPIDEH SHARIF A DISSERTATION SUBMITTED TO THE FACULTY OF GRADUATE STUDIES IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY GRADUATE PROGRAM IN CHEMISTRY YORK UNIVERSITY TORONOTO, ONTARIO FEBRUARY 2019 © SEPIDEH SHARIF 2019 ABSTRACT Among Pd-catalyzed carbon-heteroatom cross-coupling reactions, C-N bond formation, known as Buchwald-Hartwig amination (BHA), is by far the most studied reaction owing to the prevalence of arylated amines in pharmaceuticals, natural products, organic materials, and catalysts. Despite the tremendous progress that has been achieved with respect to improving the efficiency and expanding the scope of BHA of (hetero)aryl halides and amine nucleophilic partners, some challenges remain to be addressed. These challenges include selective monoarylation of primary alkyl amines, enantioretentive N-arylation of a-amino esters and arylation of amide nucleophiles. This research is mainly focused on evaluating the reactivity of Pd-NHC pre-catalysts, in particular Pd-PEPPSI (Pyridine Enhanced Pre-catalyst Preparation Stabilization and Initiation) complexes in such challenging BHA reactions. Pd-PEPPSI-IPentCI, was identified as one of the most reactive and selective pre-catalysts yet reported in the literature in the arylation of primary alkyl amines. The high level of selectivity that was exhibited by Pd-PEPPSI-IPentCI is assured by the use of the mild, soluble and sterically demanding sodium salt of butylated hydroxytoluene (NaBHT) as the base in this transformation. Pd-PEPPSI-IPentCl-o-picoline was shown to effectively couple a variety of amino acids as the tert-butyl ester with heteroaryl chlorides in high yields and with excellent stereoretention of the acidic proton adjacent to the ester.
    [Show full text]
  • PALLADIUM-PEPPSI-Ipentcl; a USEFUL CATALYST for CHALLENGING AMINATION REACTIONS
    PART I: PALLADIUM-PEPPSI-IPENTCl; A USEFUL CATALYST FOR CHALLENGING AMINATION REACTIONS PART II: GENERATION OF BENZYNES IN FLOW REACTORS FOLLOWED BY SUBSEQUENT DIELS-ALDER REACTIONS ABIR ALI KHADRA A DISSERTATION SUBMITTED TO THE FACULTY OF GRADUATE STUDIES IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY GRADUATE PROGRAM IN CHEMISTRY YORK UNIVERSITY TORONTO, CANADA MAY, 2018 © ABIR ALI KHADRA, 2018 ABSTRACT: The first part of this research focuses on developing efficient methods to address challenging Buchwald –Hartwig amination reactions using Pd-NHC pre-catalysts. Specifically, we focused on: a) coupling of sterically hindered primary and secondary amines and b) coupling of 2-aminopyridine derivatives with aryl and heteroaryl halides. Although several approaches have been developed and proven to be effective for coupling of sterically hindered amines, they have limited utility and substrate scope. Pd-PEPPSI-IPentCl (Pyridine Enhanced Pre-catalyst Preparation Stabilization and Initiation) proved to be a very effective catalyst for coupling hindered primary and secondary amines under mild reaction conditions (i.e. Na-BHT (BHT = 2,6-Di-tert-butyl hydroxyl toluene), 80 °C, DME) tolerating base sensitive functional groups such as ester, keto, and nitrile groups. While the synthesis of 2-aminopyridine derivatives is commonly carried out by metal-catalyzed coupling of 2-halopyridines with aniline derivatives, the use of 2-aminopyridine as a nucleophilic partner in Pd catalysis is very difficult as these substrates tend to bind irreversibly to the palladium center and shut down the catalytic cycle. However, Pd-PEPPSI-IPentCl has been found to resist the binding of 2-aminopyridines, making it a very active catalyst for these couplings.
    [Show full text]
  • Cross Coupling Reactions Catalyzed by (NHC)Pd(II) Complexes
    Turkish Journal of Chemistry Turk J Chem (2015) 39: 1115 { 1157 http://journals.tubitak.gov.tr/chem/ ⃝c TUB¨ ITAK_ Review Article doi:10.3906/kim-1510-31 Cross coupling reactions catalyzed by (NHC)Pd(II) complexes Nevin GURB¨ UZ¨ 1, Emine Ozge¨ KARACA1, Ismail_ OZDEM¨ IR_ 1;∗, Bekir C¸ETINKAYA_ 2;∗ 1Catalysis Research and Application Center, In¨on¨uUniversity,_ Malatya, Turkey 2Department of Chemistry, Ege University, Bornova, Izmir,_ Turkey Received: 13.10.2015 • Accepted/Published Online: 17.11.2015 • Printed: 25.12.2015 Abstract: This review is focused on new developments reported during the last 3 years concerning the catalytic performances of in situ formed or preformed NHC{Pd(II) complexes (NHC: N -heterocyclic carbene) for cross-coupling reactions such as Heck{Mizoraki (often shortened to the Heck reaction), Kumada, Negishi, Suzuki{Miyaura (often shortened to the Suzuki reaction), Sonogashira and Hiyama couplings, and the Buchwald{Hartwig aminations, which are extremely powerful in the formation of C{C and C{heteroatom bonds. Due to the great number of publications and limited space here, we made a special attempt to compile the relevant data in tables, which we hope will serve as a guide for chemists interested in these reactions. The syntheses of the precatalysts and the generally accepted reaction mechanisms are also briefly described. Key words: N -heterocyclic carbene, palladium, cross-coupling reaction 1. Introduction The awarding of the 2010 Nobel Prize jointly to Heck, Suzuki, and Negishi clearly reflects the importance of palladium-catalyzed cross-coupling reactions in chemistry. 1 They provide chemists with a very versatile tool for the construction of carbon{carbon and carbon{heteroatom bonds in the synthesis of pharmaceuticals, agrochemicals, and organic electronic materials.
    [Show full text]
  • Complex and Its Efficiency As a Catalyst for Mizoroki-Heck Cross-Coupling
    J. Chem. Sci. Ó (2020) 132:51 Indian Academy of Sciences https://doi.org/10.1007/s12039-020-1754-y Sadhana(0123456789().,-volV)FT3](0123456789().,-volV) REGULAR ARTICLE A new PEPPSI type N-heterocyclic carbene palladium(II) complex and its efficiency as a catalyst for Mizoroki-Heck cross-coupling reactions in water DHRUBAJIT BORAHa,b , BISWAJIT SAHAc,d , BIPUL SARMAe and PANKAJ DASa,* aDepartment of Chemistry, Dibrugarh University, Dibrugarh, Assam 786004, India bDepartment of Chemistry, N. N. Saikia College, Titabar, Assam 785630, India cAdvanced Materials Group, Materials Sciences and Technology Division, CSIR-North East Institute of Science and Technology, Jorhat, Assam 785006, India dAcademy of Scientific and Innovative Research (AcSIR), CSIR-NEIST Campus, Jorhat, Assam 785006, India eDepartment of Chemical Sciences, Tezpur University, Napaam, Tezpur, Assam 784028, India E-mail: [email protected] MS received 29 August 2019; revised 7 November 2019; accepted 10 November 2019 Abstract. A new air and moisture stable PEPPSI (PEPPSI: pyridine-enhanced pre-catalyst preparation, stabilisation, and initiation) themed palladium N-heterocyclic carbene (NHC) complex [Pd(L)Br2(Py)] (1) [L: 2-flurobenzyl)-1-(4-methoxyphenyl)-1H-imidazolline-2-ylidene] was synthesized and characterized. The structure of complex 1 was determined by X-ray single-crystal analysis. The palladium center in 1 adopted a square planar geometry with carbene and pyridine ligands occupying the mutual trans position. The complex 1 was employed to catalyze the Mizoroki-Heck cross-coupling reactions of aryl bromides/iodides with styrene in water. To the best of our knowledge, this is the first report where a Pd-PEPPSI catalyst was successfully employed in aqueous-phase Mizoroki-Heck reaction.
    [Show full text]
  • Enhanced Precatalyst Preparation Stabilization and Initiation (EPPSI) Nano Molecules
    Opinion Metabolomics: Volume 11:1, 2021 Open Access ISSN: 2153-0769 Open Access Putrescine, Cadaverine, Spermine and Spermidine- Enhanced Precatalyst Preparation Stabilization and Initiation (EPPSI) Nano Molecules Ricardo Gobato1, Alireza Heidari2* 1Green Land Landscaping and Gardening, Seedling Growth Laboratory, 86130-000, Parana, Brazil 2Faculty of Chemistry, California South University, 14731 Comet St. Irvine, CA 92604, USA Keywords: Putrescine • Cadaverine • Spermine Opinion relatively easy to synthesize and handle.In this work, the term Enhanced Precatalyst Preparation Stabilization and Initiation (EPPSI) is used.In the basic structure of PEPPSI, R can be a methyl (CH , Me), ethyl (C H , Et), In the current study, we study Putrescine, Cadaverine, Spermine and 3 2 5 isopropyl (C H , iPr), isopentyl (C H , iPent), or isoheptyl (C H , iHept) Spermidine–Enhanced Precatalyst Preparation Stabilization and Initiation 3 7 5 11 7 15 group, and the resulting catalysts are thus labeled as PEPPSI-IMes, (EPPSI) Nano molecules incorporation into the Nano Polymeric Matrix PEPPSI-IEt, PEPPSI-IPr, PEPPSI-IPent, and PEPPSI-IHept respectively, (NPM) by immersion of the Nano Polymeric Modified Electrode (NPME) with or without "Pd-" added in front. Contrary to common palladium-based as molecular enzymes and drug targets for human cancer cells, tissues catalysts, such as tetrakis(triphenylphosphine)palladium(0), PEPPSI is and tumors treatment under synchrotron and synchrocyclotron radiations. stable to exposure to air and moisture. Even heating in dimethyl sulfoxide at Putrescine is related to cadaverine (both polyamine). Both are produced 120°C for hours does not result in significant decomposition or neutralization by the breakdown of amino acids in living and dead organisms and both of PEPPSI catalysts.
    [Show full text]
  • Aminomethylpyridinequinones As New Ligands for PEPPSI-Type Complexes
    The Free Internet Journal Paper for Organic Chemistry Archive for Arkivoc 2021, part iii, 0-0 Organic Chemistry to be inserted by editorial office Aminomethylpyridinequinones as new ligands for PEPPSI-type complexes Roman Gajda,a Albert Poater,b Artur Brotons-Rufes,b Sebastian Planer,a Krzysztof Woźniak,a Karol Grela,a and Anna Kajetanowicza,c,* a Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089 Warsaw, Poland b Institut de Química Computacional i Catàlisi, Departament de Química, University of Girona, c/ Maria Aurèlia Capmany 69, Girona 17003, Catalonia, Spain c Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland Email: [email protected] Dedicated to Professor Lanny Liebeskind Received mm-dd-yyyy Accepted mm-dd-yyyy Published on line mm-dd-yyyy Dates to be inserted by editorial office Abstract A set of six new catalysts possessing quinone moieties in a pyridine ligand was synthesized and fully characterized by standard analytical techniques, including X-Ray crystallography. The results obtained in Suzuki and Mizoroki–Heck cross-coupling reactions catalyzed by quinone-based compounds were comparable to these obtained in the presence of the original PEPPSI complex designed by Organ. DFT calculations allow us to see the structural and electronic factors to describe their similarity. On the other hand, steric maps and NCI plots were the tools to have a more global view of the systems studied, leaving the sphere of reactivity around the metal. Keywords: Cross-coupling, PEPPSI, pyridine, quinones, NHC DOI: https://doi.org/10.24820/ark.5550190.p011.451 Page 1 ©AUTHOR(S) Arkivoc 2021, iii, 0-0 Gajda, R.
    [Show full text]
  • Uppsala University
    Uppsala University Project Thesis Suzuki coupling of functionalized arylboronic acids to a 2-Amino-5-(4-bromophenyl)-1,3,4-thiadiazole scaffold Supervisors: Author: Dr. Wei Berts Fredric Ingner Dr. Jonas Malmström February 21, 2015 Abstract Seven arylboronic acids, all but one containing functional groups, were cho- sen for Suzuki cross coupling to a predetermined scaffold for a contract project. The scaffold was synthesized and catalytic ability was assesed for three palla- dium catalysts: Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), (1,1’- Bis(diphenylphosphino)ferrocene)palladium(II) dichloride (Pd(DPPF)Cl2) and PEPPSI-iPr. Library reactions proceeded with Tetrakis since it was found to be the only catalyst capable of producing product during trials. All reactions were worked up by flash chromatography, except one where preperative HPLC had to be used. Reactions and purification steps were analyzed crudely with TLC and more thoroughly through LC-MS with ESI. Structural analysis in form of 1H-NMR was made of the scaffold and two products. It was found that all but one of the seven reactions proceeded to completion with 0.1 eq of catalyst under alkali conditions at 80o C. 1 Acknowledgements I would like to thank Dr. Fredrik Lehmann for allowing me to do my thesis work at OnTarget Chemistry. I am very grateful to have been supervised by Dr. Wei Berts and Dr. Jonas Malmström, without whom this thesis would not have been possible. I also extend my gratitude to all of the employees of OnTarget Chemistry who have made me feel very much at home and as a part of the team.
    [Show full text]
  • Catalysis PEPPSI™ Catalyst
    Vol. 6 No. 3 Catalysis PEPPSI™ Catalyst General Background Advantages of PEPPSI™ Reaction Types · Negishi · Suzuki · Buchwald–Hartwig · Kumada Future Generation PEPPSI™ sigma-aldrich.com General Background Palladium has played a central role in the expeditious preparation of complex organic Vol. 6 No. 3 molecules, since the discovery and subsequent catalytic use of Pd(PPh3)4 by Malatesta, Angoletta and others.1 In the world of catalysis, the ancillary ligands of any Pd complex represent the chassis, whereas the Pd center functions as the driver for cross-coupling Aldrich Chemical Co., Inc. reactions. These metal-catalyzed processes arguably remain the most powerful means Sigma-Aldrich Corporation to generate C–C, C–O, and C–N bonds in the synthetic chemist’s toolbox.2,3 Catalyst 6000 N. Teutonia Ave. developments in the cross-coupling field have been concentrated in rapid design and deployment of complexes containing tertiary phosphine ligands. The disadvantages of Milwaukee, WI 53209, USA utilizing phosphines as ligands for Pd are numerous, including their high expense, sensitivity, and lack of commercial sources for late generation compounds. Perhaps most importantly, few catalysts exhibit superior activity among broad substrate classes and reaction paradigms. To Place Orders It should also be noted that Pd(PPh3)4 is widely applied in catalysis, but this complex suffers Telephone 800-325-3010 (USA) from poor stability upon storage as well as advised handling under nitrogen. FAX 800-325-5052 (USA) N-Heterocyclic carbene (NHC) Pd complexes have been designed in order to overcome some of these limitations.4 Professor Mike Organ at York University, along with co- Customer & Technical Services workers Dr.
    [Show full text]