文献类型：期刊文献

英文题名：Rhodium/Silver Synergistic Catalysis in Highly Enantioselective Cycloisomerization/Cross Coupling of Keto-Vinylidenecyclopropanes with Terminal Alkynes

作者：Yang, Song[1,2];Rui, Kang-Hua[1,2];Tang, Xiang-Ying[5];Xu, Qin[1,2];Shi, Min[1,2,3,4,5]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, 130 Mei Long Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Inst Fine Chem, 130 Mei Long Rd, Shanghai 200237, Peoples R China;[3]Nankai Univ, Collaborat Innovat Ctr Chem Sci & Engn Tianjin, State Key Lab, Tianjin 300071, Peoples R China;[4]Nankai Univ, Collaborat Innovat Ctr Chem Sci & Engn Tianjin, Inst Element Organ Chem, Tianjin 300071, Peoples R China;[5]Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 354 Fenglin Rd, Shanghai 200032, Peoples R China

年份：2017

卷号：139

期号：16

起止页码：5957

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20171803626384);WOS:【SCI-EXPANDED(收录号:WOS:000400321500055)，CCR-EXPANDED(收录号:WOS:000400321500055)】；

基金：We are grateful for the financial support from the National Basic Research Program of China (973)-2015CB856603, the Strategic Priority Research Program of the Chinese Academy of Sciences, grant no. XDB20000000, the National Natural Science Foundation of China (20472096, 21372241, 21572052, 20672127, 21421091, 21372250, 21121062, 21302203, and 20732008), and the Fundamental Research Funds for the Central Universities 222201717003.

语种：英文

外文关键词：Enantioselectivity - Silver compounds - Isomerization - Rhodium compounds - Hydrocarbons

摘要：A rhodium/silver synergistic catalysis has been established, enabling cycloisomerization/cross coupling of keto-vinylidenecyclopropanes (VDCPs) with terminal alkynes toward the regio- and enantioselective formation of diversified tetrahydropyridin-3-ol tethered 1,4-enynes in good yields and high ee values. In this synergistic catalysis, Rh(I) and Ag(I) catalysts selectively activate keto-VDCP substrates and terminal alkynes to generate the pi-allyl Rh(III) complex of oxa-rhodacyclic intermediate and Ag alkynyl intermediate, respectively. The rapid transmetalation of alkynyl groups from Ag to Rh is proposed to play a key role in realizing the regioselective cleavage of the distal bond of the three-membered ring in this transformation.