title: Enantioselective Rhodium-Catalyzed Cycloisomerization of (E)-1,6-Enynes.
abstract: An enantioselective rhodium(I)-catalyzed cycloisomerization reaction of challenging (E)-1,6-enynes is reported. This novel process enables (E)-1,6-enynes with a wide range of functionalities, including nitrogen-, oxygen-, and carbon-tethered (E)-1,6-enynes, to undergo cycloisomerization with excellent enantioselectivity, in a high-yielding and operationally simple manner. Moreover, this Rh(I) -diphosphane catalytic system also exhibited superior reactivity and enantioselectivity for (Z)-1,6-enynes. A rationale for the striking reactivity difference between (E)- and (Z)-1,6-enynes using Rh(I) -BINAP and Rh(I) -TangPhos is outlined using DFT studies to provide the necessary insight for the design of new catalyst systems and the application to synthesis.
authors.affiliation: Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, P.R. China.
authors.forename: Xu
authors.initials: X
authors.lastname: Deng
authors.affiliation: Department of Chemistry, South University of Science and Technology of China, 518055, Shenzhen, P.R. China.
authors.forename: Shao-Fei
authors.initials: SF
authors.lastname: Ni
authors.affiliation: Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, P.R. China.
authors.forename: Zheng-Yu
authors.initials: ZY
authors.lastname: Han
authors.affiliation: Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, P.R. China.
authors.forename: Yu-Qing
authors.initials: YQ
authors.lastname: Guan
authors.affiliation: Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, P.R. China.
authors.forename: Hui
authors.initials: H
authors.lastname: Lv
authors.affiliation: Department of Chemistry, South University of Science and Technology of China, 518055, Shenzhen, P.R. China. dangl@sustc.edu.cn.
authors.forename: Li
authors.initials: L
authors.lastname: Dang
authors.affiliation: Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, P.R. China. xumu@whu.edu.cn.
authors.forename: Xu-Mu
authors.initials: XM
authors.lastname: Zhang
keywords: (E)-1,6-enyne; TangPhos; asymmetric synthesis; cycloisomerization; rhodium catalysis