A Boron-Nitrogen Double Transborylation Strategy for Borane-Catalyzed Hydroboration of Nitriles.

Organoborane-catalyzed hydroboration of nitriles provides N , N -diborylamines, which act as efficient synthons for the synthesis of primary amines and secondary amides. Known nitrile hydroboration methods are dominated by metal catalysis. Simple and metal-free hydroboration of nitriles using diborane [H-B-9-BBN] 2 as a catalyst and pinacolborane as a turnover reagent is reported. The reaction of monomeric H-B-9-BBN with nitriles leads to the hydrido-bridged diborylimine intermediate; a subsequent sequential double hydroboration-transborylation pathway involving B-N/B-H σ bond metathesis is proposed.