Mechanistic Studies on a Cooperative NHC Organocatalysis/Palladium Catalysis System: Uncovering Significant Lessons for Mixed Chiral Pd(NHC)(PR3) Catalyst Design

被引：171
作者：
Guo, Chang [1 ]
Janssen-Mueller, Daniel [1 ]
Fleige, Mirco [1 ]
Lerchen, Andreas [1 ]
Daniliuc, Constantin G. [1 ]
Glorius, Frank [1 ]
机构：
[1] Westfal Wilhelms Univ Munster, Inst Organ Chem, Corrensstr 40, D-48149 Munster, Germany
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 12期
关键词：
N-HETEROCYCLIC CARBENE; TRANSITION-METAL CATALYSIS; MONODENTATE P-LIGANDS; DIELS-ALDER REACTION; ASYMMETRIC HYDROGENATION; OLEFIN HYDROGENATION; ENANTIOSELECTIVE HYDROGENATION; PHOTOREDOX CATALYSIS; GAMMA-BUTYROLACTONES; ALLYLIC ALKYLATION;
D O I：
10.1021/jacs.7b00462
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A comprehensive investigation of the mechanism of the highly enantioselective Pd(PPh3)(4)/NHC-catalyzed annulation of vinyl benzoxazinanones and enals has been conducted. A study of reaction orders supports the postulated cooperative catalysis. Interestingly, a detailed investigation of the catalytically active palladium species pointed toward a dual role of the NHC acting as an organocatalyst and forming a novel mixed ligand Pd/NHC/phosphine complex. The catalytically active Pd/NHC/phosphine complex represents a new class of chiral palladium catalyst. Remarkably, phosphine plays a crucial role in this transformation. These complexes could be characterized by X-ray crystallographic analysis and employed as catalysts for the enantioselective [4 + 1] annulation reaction of vinyl benzoxazinones and sulfur ylides in good yields and good enantioselectivities.
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收藏
页码：4443 / 4451
页数：9
相关论文
共 72 条
  • [1] Insight into the mechanism of the asymmetric ring-opening aminolysis of 4,4-dimethyl-3,5,8-trioxabicyclo[5.1.0]octane catalyzed by titanium/BINOLate/water system:: Evidence for the Ti(BINOLate)2-bearing active catalyst entities and the role of water
    Bao, Hongli
    Zhou, Jing
    Wang, Zheng
    Guo, Yinlong
    You, Tianpa
    Ding, Kuiling
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (31) : 10116 - 10127
  • [2] Extending NHC-Catalysis: Coupling Aldehydes with Unconventional Reaction Partners
    Biju, Akkattu T.
    Kuhl, Nadine
    Glorius, Frank
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 2011, 44 (11) : 1182 - 1195
  • [3] A mixed-ligand approach enables the asymmetric hydrogenation of an α-isopropylcinnamic acid en route to the renin inhibitor aliskiren
    Boogers, Jeroen A. F.
    Felfer, Ulfried
    Kotthaus, Martina
    Lefort, Laurent
    Steinbauer, Gerhard
    de Vries, Andre H. M.
    de Vries, Johannes G.
    [J]. ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2007, 11 (03) : 585 - 591
  • [4] Organocatalytic umpolung: N-heterocyclic carbenes and beyond
    Bugaut, Xavier
    Glorius, Frank
    [J]. CHEMICAL SOCIETY REVIEWS, 2012, 41 (09) : 3511 - 3522
  • [5] Organocatalyzed conjugate umpolung of α,β-unsaturated aldehydes for the synthesis of γ-butyrolactones
    Burstein, C
    Glorius, F
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (45) : 6205 - 6208
  • [6] Asymmetric Organocatalysis Combined with Metal Catalysis: Concept, Proof of Concept, and Beyond
    Chen, Dian-Feng
    Han, Zhi-Yong
    Zhou, Xiao-Le
    Gong, Liu-Zhu
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 2014, 47 (08) : 2365 - 2377
  • [7] Palladium-catalyzed allylic alkylation of tert-butyl(diphylmethylene)-glycinate with simple allyl esters under chiral phase transfer conditions
    Chen, GS
    Deng, YJ
    Gong, LZ
    Mi, AQ
    Cui, X
    Jiang, YZ
    Choi, MCK
    Chan, ASC
    [J]. TETRAHEDRON-ASYMMETRY, 2001, 12 (11) : 1567 - 1571
  • [8] Cooperative Lewis acid/N-heterocyclic carbene catalysis
    Cohen, Daniel T.
    Scheidt, Karl A.
    [J]. CHEMICAL SCIENCE, 2012, 3 (01) : 53 - 57
  • [9] Cole R.B., 1997, ELECTROSPRAY IONIZAT
  • [10] N-Heterocyclic Carbenes in Late Transition Metal Catalysis
    Diez-Gonzalez, Silvia
    Marion, Nicolas
    Nolan, Steven P.
    [J]. CHEMICAL REVIEWS, 2009, 109 (08) : 3612 - 3676
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