Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C-H functionalization

Yang Zheng; Wen-Yun Zhang; Qing Gu; Chao Zheng; Shu-Li You

doi:10.1038/s41467-023-36723-6

Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C-H functionalization

Nat Commun. 2023 Feb 25;14(1):1094. doi: 10.1038/s41467-023-36723-6.

Authors

Yang Zheng¹, Wen-Yun Zhang¹, Qing Gu¹, Chao Zheng², Shu-Li You³

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
² State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China. zhengchao@sioc.ac.cn.
³ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China. slyou@sioc.ac.cn.

Abstract

Asymmetric ring-opening of 7-oxabenzonorbornadienes is achieved via Co-catalyzed indole C-H functionalization. The utilization of chiral Co-catalyst consisting of a binaphthyl-derived trisubstituted cyclopentadienyl ligand resulted in high yields (up to 99%) and excellent enantioselectivity (>99% ee) for the target products with tolerance for diverse functional groups. Opposite diastereoselectivities are obtained with chiral Co-catalyst or Cp*CoI₂CO. Combined experimental and computational studies suggest β-oxygen elimination being the selectivity-determining step of the reaction. Meanwhile, the reactions of 7-azabenzonorbornadiene could also be executed in a diastereodivergent manner.