Visible Light-Induced Halogen-Atom Transfer by N-Heterocyclic Carbene-Ligated Boryl Radicals for Diastereoselective C(sp3)–C(sp2) Bond Formation

Photoinduced Halogen-Atom Transfer (XAT) has rapidly emerged as a programmable approach to generate carbon-centered radical intermediates, mainly relying on silyl and α-aminoalkyl radicals as halogen abstractors. More recently, ligated boryl radicals have also been proposed as effective halogen abstractors under visible-light irradiation. In this study, we describe the use of this approach to enable C(sp3)–C(sp2) bond formation via radical addition of carbon-centered radicals generated via XAT onto chloroalkynes. Our mechanistic investigation reveals a complex interplay of highly reactive radical intermediates which, under optimized conditions, delivered the targeted vinyl chlorides in excellent yields and Z:E ratios. Finally, we demonstrated the synthetic value of these products in transition metal-based cross-coupling reactions.