Enantioselective Rhodium-Catalyzed Cycloisomerization of (E)-1,6-Enynes

Xu Deng; Shao-Fei Ni; Zheng-Yu Han; Yu-Qing Guan; Hui Lv; Li Dang; Xu-Mu Zhang

doi:10.1002/anie.201601061

Enantioselective Rhodium-Catalyzed Cycloisomerization of (E)-1,6-Enynes

Angew Chem Int Ed Engl. 2016 May 17;55(21):6295-9. doi: 10.1002/anie.201601061. Epub 2016 Apr 9.

Authors

Xu Deng¹, Shao-Fei Ni², Zheng-Yu Han¹, Yu-Qing Guan¹, Hui Lv¹, Li Dang³, Xu-Mu Zhang⁴

Affiliations

¹ Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, P.R. China.
² Department of Chemistry, South University of Science and Technology of China, 518055, Shenzhen, P.R. China.
³ Department of Chemistry, South University of Science and Technology of China, 518055, Shenzhen, P.R. China. dangl@sustc.edu.cn.
⁴ 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.

PMID: 27061132
DOI: 10.1002/anie.201601061

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.

Keywords: (E)-1,6-enyne; TangPhos; asymmetric synthesis; cycloisomerization; rhodium catalysis.

Publication types

Research Support, Non-U.S. Gov't