Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydrofunctionalization and Formal Retro-hydrofunctionalization.
- Author(s): Hanna, Steven;
- Butcher, Trevor W;
- Hartwig, John F
- et al.
Published Web Locationhttps://doi.org/10.1021/acs.orglett.9b02695
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.