Copper-catalyzed enantioselective diyne cyclization via C(sp2)-O bond cleavage

Ji-Jia Zhou; Ya-Nan Meng; Li-Gao Liu; Yi-Xi Liu; Zhou Xu; Xin Lu; Bo Zhou; Long-Wu Ye

doi:10.1039/d2sc06152j

Copper-catalyzed enantioselective diyne cyclization via C(sp²)-O bond cleavage

Chem Sci. 2023 Mar 1;14(13):3493-3500. doi: 10.1039/d2sc06152j. eCollection 2023 Mar 29.

Authors

Ji-Jia Zhou¹, Ya-Nan Meng¹, Li-Gao Liu¹, Yi-Xi Liu¹, Zhou Xu², Xin Lu¹, Bo Zhou¹, Long-Wu Ye^{1

3}

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 China longwuye@xmu.edu.cn xinlu@xmu.edu.cn xuzhou@xzhmu.edu.cn.
² Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University Xuzhou 221004 China.
³ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Shanghai 200032 China.

Abstract

The functionalization of etheric C-O bonds via C-O bond cleavage is an attractive strategy for the construction of C-C and C-X bonds in organic synthesis. However, these reactions mainly involve C(sp³)-O bond cleavage, and a catalyst-controlled highly enantioselective version is extremely challenging. Here, we report a copper-catalyzed asymmetric cascade cyclization via C(sp²)-O bond cleavage, allowing the divergent and atom-economic synthesis of a range of chromeno[3,4-c]pyrroles bearing a triaryl oxa-quaternary carbon stereocenter in high yields and enantioselectivities. Importantly, this protocol not only represents the first [1,2]-Stevens-type rearrangement via C(sp²)-O bond cleavage, but also constitutes the first example of [1,2]-aryl migration reactions via vinyl cations.