Radical 1,2-Boron Shift-Enabled Synthesis of β-Thioalkylboronic Esters from β-Boryl NHPI Esters

A novel protocol for synthesizing β-thioalkylboronic esters via decarboxylative functionalization of β-boronic acid-derived N-hydroxyphthalimide (NHPI) esters is reported. This transformation proceeds under mild conditions with a broad substrate scope and facilitates versatile product derivatization. Mechanistic investigations confirm a radical-mediated 1,2-boron migration pathway. This strategy extends the synthetic utility of radical 1,2-boron migrations from predominant C(sp3)–C bond formation to C(sp3)–S bond construction, thereby diversifying the reaction landscape of boron migration chemistry.