Copper-Catalyzed Chemo- and Enantioselective Radical 1,2-Carbosulfenylation of Diverse Alkenes with Broad Radical and Sulfur Compatibility

Abstract Enantioselective copper-catalyzed intermolecular radical 1,2-carbosulfenylation of alkenes with readily available alkyl halides provides efficient access to α-chiral alkyl organosulfur compounds, but its development has been hampered by competing side pathways and challenges in enantiocontrol. Herein, we report a general and versatile copper-catalyzed platform for chemo- and enantioselective radical 1,2-carbosulfenylation of a diverse range of alkenes. Central to this strategy is the development of a tunable and readily accessible library of multidentate anionic N,N,N(P)-ligands, which promote the desired transformation while suppressing competing radical pathways, thereby enabling broad compatibility with various alkyl radical precursors and transformable sulfur nucleophiles. The protocol exhibits a broad substrate scope, accommodating electronically diverse alkenes, including monosubstituted and 1,1-disubstituted acrylamides, as well as aryl- or heteroaryl-substituted alkenes, along with alkyl bromides and chlorides as radical precursors. The resulting products can be readily converted into a range of enantioenriched alkyl sulfur-containing building blocks of value in organic synthesis and related fields.