Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals

• Published in: Angewandte Chemie International Edition Vol. 55; no. 23; pp. 6776 - 6779
• Main Authors: Fava, Eleonora, Millet, Anthony, Nakajima, Masaki, Loescher, Sebastian, Rueping, Magnus
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 01.06.2016; Wiley; John Wiley and Sons Inc
• Subjects: amino alcohols; Chemistry; Chemistry, Multidisciplinary; Communication; Communications; diamines; photocatalysis; Physical Sciences; redox chemistry; Science & Technology; umpolung; ORGANIC-SYNTHESIS; ALPHA,BETA-UNSATURATED KETONES; umpolung; BETA-ACTIVATION; amino alcohols; C-H BONDS; redox chemistry; FUNCTIONALIZATION; MANNICH REACTION; SYNTHETIC APPLICATIONS; MICHAEL ACCEPTORS; photocatalysis; CYCLIZATION; diamines
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201511235

Visible‐light‐mediated photoredox‐catalyzed aldimine–aniline and aldehyde–aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α‐amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2‐diamines and amino alcohols. Anilines can be coupled with aldimines or aldehydes in a visible‐light‐mediated photoredox‐catalyzed process. Reductive single electron transfer (SET) umpolung of the carbonyl derivatives leads to the generation of intermediary ketyl and α‐amino radical anions, which were used for the synthesis of unsymmetrically substituted 1,2‐diamines and amino alcohols.