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A Photochemical Organocatalytic Strategy for the α-Alkylation of Ketones using Radicals.

07:00 EST 13th February 2020 | BioPortfolio

Summary of "A Photochemical Organocatalytic Strategy for the α-Alkylation of Ketones using Radicals."

Reported herein is a visible-light-mediated radical approach to the α-alkylation of ketones. This method exploits the ability of a nucleophilic organocatalyst to generate radicals upon S N 2-based activation of alkyl halides and blue light irradiation. The resulting open-shell intermediates are then intercepted by weakly nucleophilic silyl enol ethers, which would be unable to directly attack the alkyl halides through a traditional two-electron path. The method's mild reaction conditions allowed us to functionalize the α position of ketones with functional groups that are not compatible with classical anionic strategies. In addition, the redox-neutral nature of this process makes it compatible with a cinchona-based primary amine catalyst, which was used to develop a rare example of enantioselective organocatalytic radical α-alkylation of ketones.

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Name: Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
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