title: Rhodium/Silver Synergistic Catalysis in Highly Enantioselective Cycloisomerization/Cross Coupling of Keto-Vinylidenecyclopropanes with Terminal Alkynes.
abstract: 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 π-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.
authors.affiliation: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology , 130 Mei-Long Road, Shanghai 200237, China.
authors.forename: Song
authors.initials: S
authors.lastname: Yang
authors.affiliation: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology , 130 Mei-Long Road, Shanghai 200237, China.
authors.forename: Kang-Hua
authors.initials: KH
authors.lastname: Rui
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences , 354 Fenglin Road, Shanghai 200032, China.
authors.forename: Xiang-Ying
authors.initials: XY
authors.lastname: Tang
authors.affiliation: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology , 130 Mei-Long Road, Shanghai 200237, China.
authors.forename: Qin
authors.initials: Q
authors.lastname: Xu
authors.affiliation: Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology , 130 Mei-Long Road, Shanghai 200237, China.|State Key Laboratory and Institute of Element-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, China.|State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences , 354 Fenglin Road, Shanghai 200032, China.
authors.forename: Min
authors.identifier: 0000-0003-0016-5211
authors.initials: M
authors.lastname: Shi