Hydrodecyanation of Secondary Alkyl Nitriles and Malononitriles to Alkanes using DiMeImd-BH<sub>3</sub>
Takuji Kawamoto, Kyohei Oritani, Atsushi Kawabata, Tsubasa Morioka, Hiroshi Matsubara, Akio Kamimura
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.
Topics & Concepts
AlkylChemistryMedicinal chemistryOrganic chemistryAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization MethodsCarbon dioxide utilization in catalysis