Hydrodecyanation of Secondary Alkyl Nitriles and Malononitriles to Alkanes using DiMelmd-BH3

摘要

The decyanation of secondary aliphatic nitriles and the 2-fold decyanation of malononitriles leading to alkanes in the presence of 1,3-dimethylimidazol-2-ylidene borane (diMelmd-BH3) are reported. These reactions proceed via a radical mechanism that involves the addition of a borane radical to the nitrile to form an iminyl radical, followed by cleavage of a carbon-carbon bond. Theoretical calculations suggest that the beta-cleavage of these iminyl radicals, which affords NHC-BH2CN corresponding alkyl radicals, is the rate-determining step in this reaction.