Aluminum-Catalyzed Hydroboration of Alkenes

The aluminum-catalyzed hydroboration of alkenes with HBpin is reported using simple commercially available aluminum hydride precatalysts [LiAlH4 or sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al)]. Good substrate scope and functional group tolerance is demonstrated for alkene hydroboration, and the protocol was also applied to the hydroboration of ketone, ester, and nitrile functional groups, showing the potential for wider application. The aluminum-catalyzed hydroboration is proposed to proceed by alkene hydroalumination, which generates an alkyl aluminum species that undergoes sigma-bond metathesis with HBpin to drive turnover of the catalytic cycle.