Diastereo- and enantioselective rhodium(III)-catalyzed reductive cyclization of cyclohexadienone-containing 1,6-dienes

Yun-Xuan Tan; Pei-Ying Peng; Ya-Jie Wang; Xi-Liang Liu; Wenbo Ye; Dingding Gao; Guo-Qiang Lin; Ping Tian

doi:10.1039/d1cc03645a

Diastereo- and enantioselective rhodium(III)-catalyzed reductive cyclization of cyclohexadienone-containing 1,6-dienes

Chem Commun (Camb). 2021 Sep 23;57(76):9724-9727. doi: 10.1039/d1cc03645a.

Authors

Yun-Xuan Tan^{1

2}, Pei-Ying Peng¹, Ya-Jie Wang¹, Xi-Liang Liu¹, Wenbo Ye¹, Dingding Gao¹, Guo-Qiang Lin^{1

2}, Ping Tian^{1

2}

Affiliations

¹ Shanghai Frontiers Science Center for Traditional Chinese Medicine Chemical Biology, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai 201203, China. webye@sioc.ac.cn.
² CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

PMID: 34474456
DOI: 10.1039/d1cc03645a

Abstract

A diastereo- and enantioselective rhodium(III)-catalyzed reductive cyclization of cyclohexadienone-tethered terminal alkenes and (E)-1,2-disubstituted alkenes (1,6-dienes) is reported, providing cis-bicyclic products bearing three contiguous stereocenters with good yields and high diastereo- and enantioselectivities. The kinetic resolution of the racemic precursor is also achieved with good efficiency. Moreover, a subgram-scale experiment, several transformations of the cyclization product, and one-pot preparation of bridged polycyclic frameworks are presented.