Low Barrier Hydrogenolysis of the Carbon−Heteroatom Bond As Catalyzed by HAlF₄

Abstract

Quantum chemistry calculations show that the barriers for HAlF(4)-catalyzed hydrogenolysis reactions of the carbon-heteroatom bond are reduced substantially compared with those for the uncatalyzed reactions. For example, the condensed-phase free-energy barrier for the HAlF(4)-catalyzed hydrogenolysis of CH(3)-F is about 130 kJ mol(-1), compared with 373 kJ mol(-1) for the uncatalyzed reaction. The reactions are facilitated in the case of substrates that can give rise to a stable carbocation and for strongly acidic catalysts.