Categories: C-H Bond Formation >
A rhodium-catalyzed reductive cleavage of carbon-cyano bonds using hydrosilane as a mild reducing agent allows the decyanation of a wide range of nitriles, including aryl, benzyl, and β-hydrogen containing alkyl cyanides. The use of benzyl cyanide as a benzyl anion equivalent and the use of a cyano group as a removable ortho-directing group are demonstrated.
M. Tobisu, R. Nakamura, Y. Kita, N. Chatani, J. Am. Chem. Soc., 2008, 131, 3174-3175.
Single-electron-transfer conditions using Na/15-crown-5/H2O enable a reductive cleavage of unactivated carbon-cyano bonds in aliphatic nitriles. Compared with the Na/NH3 electride system generated under traditional Birch conditions, this ammonia-free electride system is more practical and features better reactivity and chemoselectivity.
Y. Ding, S. Luo, L. Ma, J. An, J. Org. Chem., 2019, 84, 15827-15833.
The use of 1,3-dimethylimidazol-2-ylidene borane (diMeImd-BH3) enables a decyanation of secondary aliphatic nitriles and a 2-fold decyanation of malononitriles leading to alkanes.
T. Kawamoto, K. Oritani, A. Kawabata, T. Morioka, H. Matsubara, A. Kamimura, J. Org. Chem., 2020, 85, 6137-6142.