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DOI: 10.1055/a-2467-4789
Photocatalytic Functionalization of Weakly Nucleophilic Alkenes with Electrophiles
Photocatalytic Generation of Alkyl Carbanions from Aryl Alkenes.
Nat. Catal. 2024;
DOI: 10.1038/s41929-024-01237-x
Keywords
C–C bond formation - alkyl carbanions - photoredox catalysis - hydroalkoxylation - hydroamidation - aminoalkylation - carboxyaminoalkylation
Significance
The Polyzos group reports a method for generating alkyl carbanions in situ from aryl alkenes using visible-light photocatalysis. This approach enables regioselective functionalization of alkenes with carbon electrophiles, producing versatile molecules like alcohols, amides, and amines without stoichiometric metal reagents. The author also highlights a mechanism involving controlled alkene radical anion formation, offering a scalable approach for diverse C–C bond formations useful in pharmaceutical synthesis.
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Comment
While alkyl carbanion equivalents provide larger structural diversity, effective catalytic approaches for their generation are still limited. In this study, the authors suggest the key to this process is the controlled formation of an alkene-derived distonic radical anion, which undergoes nucleophilic addition and a kinetically favored reductive polar crossover, producing a second carbanion primed for further functionalization.
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Publication History
Article published online:
20 December 2024
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