A metal-catalyzed new approach for α-alkynylation of cyclic amines

被引：17
作者：
Cui, Yifan [1 ,2 ]
Lin, Weilong [1 ,2 ]
Ma, Shengming [1 ,3 ]
机构：
[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Lu, Shanghai 200032, Peoples R China
[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
[3] Fudan Univ, Dept Chem, 220 Handan Lu, Shanghai 200433, Peoples R China
来源：
CHEMICAL SCIENCE | 2019年 / 10卷 / 06期
基金：
中国国家自然科学基金;
关键词：
C-H BONDS; TERMINAL ALKYNES; ENANTIOSELECTIVE APPROACH; FUNCTIONALIZATION; NITROGEN; ALLENES; ACTIVATION; ADJACENT; INDOLIZIDINE; ALKALOIDS;
D O I：
10.1039/c8sc04115f
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The first catalytic alpha-alkynylation of cyclic amines with the help of the N-propargylic group to afford 2-(1-alkynyl) N-allylic cyclic amines with an exclusive E-stereoselectivity for the in situ formed C = C bond has been realized. Based on mechanistic studies, it is proven that the reaction proceeds through metal-mediated anti-1,5-hydride transfer forming an iminonium intermediate, which accepts the addition of the in situ generated 1-alkynyl metal species. The synthetic application has also been demonstrated.
引用
收藏
页码：1796 / 1801
页数：6
相关论文
共 53 条
[1]   Synthetic Utility of Sugar-Derived Cyclic Nitrones: A Diastereoselective Synthesis of Linear 4-Azatriquinanes [J].
Bandaru, Anandaraju ;
Kaliappan, Krishna P. .
SYNLETT, 2012, (10) :1473-1476
[2]   Regioselective, diastereoselective, and enantioselective lithiation-substitution sequences: Reaction pathways and synthetic applications [J].
Beak, P ;
Basu, A ;
Gallagher, DJ ;
Park, YS ;
Thayumanavan, S .
ACCOUNTS OF CHEMICAL RESEARCH, 1996, 29 (11) :552-560
[3]   Direct sp3 C-H bond activation adjacent to nitrogen in heterocycles [J].
Campos, Kevin R. .
CHEMICAL SOCIETY REVIEWS, 2007, 36 (07) :1069-1084
[4]  
Chen WJ, 2018, NAT CHEM, V10, P165, DOI [10.1038/NCHEM.2871, 10.1038/nchem.2871]
[5]   Synthesis of N-Propargylsulfoximines by Copper-Catalyzed A3-Couplings [J].
Cheng, Hanchao ;
Wen, Jian ;
Bolm, Carsten .
CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (50) :12100-12103
[6]   Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C-C Bonds [J].
Cherney, Alan H. ;
Kadunce, Nathaniel T. ;
Reisman, Sarah E. .
CHEMICAL REVIEWS, 2015, 115 (17) :9587-9652
[7]   Selective methodologies for the synthesis of biologically active piperidinic compounds [J].
Cossy, J .
CHEMICAL RECORD, 2005, 5 (02) :70-80
[8]   Redox-Neutral Copper(II) Carboxylate Catalyzed -Alkynylation of Amines [J].
Das, Deepankar ;
Sun, Aaron X. ;
Seidel, Daniel .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (13) :3765-3769
[9]  
Doye S, 2001, ANGEW CHEM INT EDIT, V40, P3351, DOI 10.1002/1521-3773(20010917)40:18<3351::AID-ANIE3351>3.0.CO
[10]  
2-B
123456