Site- and Stereoselective Synthesis of Alkenyl Chlorides by Dual Functionalization of Internal Alkynes via Photoredox/Nickel Catalysis

Liping Huo; Xiaofang Li; Yaheng Zhao; Ling Li; Lingling Chu

doi:10.1021/jacs.3c02748

Site- and Stereoselective Synthesis of Alkenyl Chlorides by Dual Functionalization of Internal Alkynes via Photoredox/Nickel Catalysis

J Am Chem Soc. 2023 May 3;145(17):9876-9885. doi: 10.1021/jacs.3c02748. Epub 2023 Apr 18.

Authors

Liping Huo¹, Xiaofang Li¹, Yaheng Zhao¹, Ling Li¹, Lingling Chu¹

Affiliation

¹ State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Center for Advanced Low-Dimension Materials, Donghua University, Shanghai 201620, China.

PMID: 37072001
DOI: 10.1021/jacs.3c02748

Abstract

Herein, we report a redox-neutral and atom-economical protocol to synthesize valuable alkenyl chlorides from unactivated internal alkynes and abundant organochlorides via photoredox and nickel catalysis. This protocol enables the site- and stereoselective addition of organochlorides to alkynes via chlorine photoelimination-initiated sequential hydrochlorination/remote C-H functionalization. The protocol is compatible with a wide range of medicinally relevant heteroaryl, aryl, acid, and alkyl chlorides for efficiently producing γ-functionalized alkenyl chlorides, exhibiting excellent regioselectivities and stereoselectivities. Late-stage modifications and synthetic manipulations of the products and preliminary mechanistic studies are also presented.