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Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydrofunctionalization and Formal
Steven Hanna1, Trevor W Butcher1, John F Hartwig1
1Division of Chemical Sciences, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California, Berkeley, California 94720, United States.
Abstract:
We report a contra-thermodynamic isomerization of internal olefins to terminal olefins driven by redox reactions and formation of Si-F bonds. This process involves chain-walking hydrosilylation of internal olefins and subsequent formal retro-hydrosilylation. The process rests upon the high activities of platinum hydrosilylation catalysts for isomerization of metal alkyl intermediates and a new, metal-free process for the conversion of alkylsilanes to alkenes. By this approach, 1,2-disubstituted and trisubstituted olefins are converted to terminal olefins.
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