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

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.