Catalytic Ketyl-Olefin Cyclizations Enabled by Proton-Coupled Electron Transfer
Journal of the American Chemical Society2013Vol. 135(27), pp. 10022–10025
Citations Over TimeTop 1% of 2013 papers
Abstract
Concerted proton-coupled electron transfer is a key mechanism of substrate activation in biological redox catalysis. However, its applications in organic synthesis remain largely unexplored. Herein, we report the development of a new catalytic protocol for ketyl-olefin coupling and present evidence to support concerted proton-coupled electron transfer being the operative mechanism of ketyl formation. Notably, reaction outcomes were correctly predicted by a simple thermodynamic formalism relating the oxidation potentials and pKa values of specific Brønsted acid/reductant combinations to their capacity to act jointly as a formal hydrogen atom donor.
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