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Hydrodecyanation of Secondary Alkyl Nitriles and Malononitriles to Alkanes using DiMeImd-BH3
Takuji Kawamoto1, Kyohei Oritani1, Atsushi Kawabata1
1Department of Applied Chemistry, Yamaguchi University, Ube, Yamaguchi 755-8611, Japan.
Abstract:
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 (diMeImd-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 β-cleavage of these iminyl radicals, which affords NHC-BH2CN and the corresponding alkyl radicals, is the rate-determining step in this reaction.
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