Umpolung Difunctionalization of Carbonyls via Visible-Light Photoredox Catalytic Radical-Carbanion Relay.

ABSTRACT: The combination of photoredox catalysis with the Wolff-Kishner (WK) reaction allows the difunctionalization of carbonyl groups by a radical-carbanion relay sequence (photo-Wolff-Kishner reaction). Photoredox initiated radical addition to N-sulfonylhydrazones yields α-functionalized carbanions following the WK-type mechanism. With sulfur-centered radicals, the carbanions are further functionalized by reaction with electrophiles including CO₂ and aldehydes, whereas CF₃ radical addition furnishes a wide range of gem-difluoroalkenes through β-fluoride elimination of the generated α-CF₃ carbanions. More than 80 substrate examples demonstrate the broad applicability of this reaction sequence. A series of investigations including radical inhibition,

SUBMITTER: Wang S 

PROVIDER: S-EPMC7252948 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature