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Low barrier hydrogenolysis of the carbon-heteroatom bond as catalyzed by HAlF(4)
George Zhong1, Bun Chan, Leo Radom
1School of Chemistry and Center of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Sydney NSW 2006, Australia.
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.
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