Spiroketal-Based Diphosphine Ligands in Pd-Catalyzed Asymmetric Allylic Amination of Morita-Baylis-Hillman Adducts: Exceptionally High Efficiency and New Mechanism

被引:141
作者
Wang, Xiaoming [1 ]
Guo, Peihua [1 ]
Han, Zhaobin [1 ]
Wang, Xubin [1 ]
Wang, Zheng [1 ]
Ding, Kuiling [1 ]
机构
[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Oganometall Chem, Shanghai 200032, Peoples R China
关键词
TRANSITION-METAL COMPLEXES; HETEROGENEOUS CATALYSIS; BIFUNCTIONAL CATALYSIS; KINETIC RESOLUTION; GAMMA-BUTENOLIDES; BITE ANGLE; PALLADIUM; SUBSTITUTION; ALKYLATION; ACETATES;
D O I
10.1021/ja410707q
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Exceptionally high activity (with a TON up to 4750) of the palladium complexes of SKP ligand was discovered in the catalysis of asymmetric allylic amination of MBH adducts with aromatic amines. A comprehensive mechanistic study indicates that the unique structural features of the SKP ligand, with a long P center dot center dot center dot P distance in its solid-state structure, were favorable for allowing two P atoms to play a bifunctional role in the catalysis. Herein, one of the P atom forms a C-P sigma-bond with the terminal carbon atom of allyl moiety as a Lewis base, and an alternative P atom coordinates to Pd atom. The cooperative action of organo- and organometallic catalysis discovered in the present catalytic system is most likely responsible for its high activity, as well as excellent regio- and enantioselectivities. The mechanism disclosed in the present catalytic system is distinct from most of the currently recognized mechanisms for Pd-catalyzed allylic substitutions.
引用
收藏
页码:405 / 411
页数:7
相关论文
共 128 条
[71]   Chiral phosphine-catalyzed regio- and enantioselective allylic amination of Morita-Baylis-Hillman acetates [J].
Ma, Guang-Ning ;
Cao, Shu-Hua ;
Shi, Min .
TETRAHEDRON-ASYMMETRY, 2009, 20 (09) :1086-1092
[72]   Towards perfect catalytic asymmetric synthesis: Dual activation of the electrophile and the nucleophile [J].
Ma, JA ;
Cahard, D .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (35) :4566-4583
[73]   Transition metal-mediated P-C/X exchange at bound phosphine ligands (X = aryl, alkyl, NR2, OR and F):: scope and mechanisms [J].
Macgregor, Stuart A. .
CHEMICAL SOCIETY REVIEWS, 2007, 36 (01) :67-76
[74]   C(sp3)-N Bond-Forming Reductive Elimination of Amines: Reactions of Bisphosphine-Ligated Benzylpalladium(II) Diarylamido Complexes [J].
Marquard, Seth L. ;
Rosenfeld, Devon C. ;
Hartwig, John F. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (04) :793-796
[75]   Nucleophilic phosphine organocatalysis [J].
Methot, JL ;
Roush, WR .
ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (9-10) :1035-1050
[76]   Engaging zwitterions in carbon-carbon and carbon-nitrogen bond-forming reactions: A promising synthetic strategy [J].
Nair, Vijay ;
Menon, Rajeev S. ;
Sreekanth, A. R. ;
Abhilash, N. ;
Biju, A. T. .
ACCOUNTS OF CHEMICAL RESEARCH, 2006, 39 (08) :520-530
[77]   Pd-catalyzed asymmetric allylic amination of Morita-Baylis-Hillman adduct derivatives using chiral diaminophosphine oxides: DIAPHOXs [J].
Nemoto, Tetsuhiro ;
Fukuyama, Takashi ;
Yamamoto, Eri ;
Tamura, Shinji ;
Fukuda, Tomoaki ;
Matsumoto, Takayoshi ;
Akimoto, Yuichi ;
Hamada, Yasumasa .
ORGANIC LETTERS, 2007, 9 (05) :927-930
[78]   Palladium(0)-Catalyzed Intermolecular Amination of Unactivated Csp3-H Bonds [J].
Pan, Jun ;
Su, Mingjuan ;
Buchwald, Stephen L. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (37) :8647-8651
[79]   Phosphine-catalyzed allylic substitution of Morita-Baylis-Hillman acetates:: Synthesis of N-protected β-aminophosphonic acid esters [J].
Park, HaeIl ;
Cho, Chang-Woo ;
Krische, Michael J. .
JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (20) :7892-7894
[80]   Cooperative bimetallic catalysis in asymmetric transformations [J].
Park, Jongwoo ;
Hong, Sukwon .
CHEMICAL SOCIETY REVIEWS, 2012, 41 (21) :6931-6943