Photocatalyzed H₂-Acceptorless Dehydrogenative Borylation by Using Amine Borane

Catalytic dehydrogenative borylation of alkenes is arguably the most straightforward approach for synthesizing alkenyl boronates, as it eliminates the need for alkene or boranes prefunctionalizion. While transition-metal catalysis has conventionally been employed for this transformation, competitive side reactions including hydroborylation, overborylation, and regioisomer formation always exist. In this study, we present a radical approach for catalytic dehydrogenative borylation, which involves the synergistic merger of photoredox/HAT/cobalt catalysis, thereby circumventing the necessity for noble metals, sacrificial hydrogen acceptors, and high temperatures. This method employs stable and cost-effective amine borane reagents as feedstocks, resulting in the sole byproduct of H2. This dehydrogenative borylation methodology facilitates the conversion of a diverse array of functionalized alkenes into valuable organoboron reagents. Furthermore, the late-stage borylation of complex molecules demonstrates high levels of site selectivity.