Radical Chain Diversification of Alkylborons Enabled by Catechol as the Sole Activator

Heteroatom-containing motifs are ubiquitous in bioactive molecules and pharmaceuticals. We report an operationally simple and air-tolerant protocol for the installation of diverse heteroatom- and carbon-based functional groups from alkylboronic esters. This approach employs catechol as the sole activator, promoting boronic ester exchange, followed by thermal or catechol-mediated initiation to generate alkyl radicals, which efficiently couple with a broad range of PhSO₂X reagents to build C-X bonds under ambient air.