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Catalytic, contra-Thermodynamic Positional Alkene Isomerization
Name
catalytic-contra-thermodynamic-alkene-isomerization.pdf
Description
Submitted version
Size
981.36 KB
Format
Adobe PDF
Checksum (MD5)
2363e994c7cdedccd53810dbf95ee05a
Author(s)
Occhialini, Gino
Palani, Vignesh
Wendlandt, Alison E
Date Issued
January 12, 2022
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Occhialini, Gino, Palani, Vignesh and Wendlandt, Alison E. 2022. "Catalytic, contra-Thermodynamic Positional Alkene Isomerization." Journal of the American Chemical Society, 144 (1).
Version
Original manuscript
Abstract
The positional isomerization of C═C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here, we report the discovery of a dual catalyst system that promotes contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing access to terminal alkene isomers directly from conjugated, internal alkene starting materials. The utility of the method is demonstrated in the deconjugation of diverse electron-rich/electron-poor alkenes and through strategic application to natural product synthesis. Mechanistic studies are consistent with a regiospecific bimolecular homolytic substitution (SH2') mechanism proceeding through an allyl-cobaloxime intermediate.
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
10.1021/jacs.1c12043
