Redox-Neutral α-Allylation of Amines by Combining Palladium Catalysis and Visible-Light Photoredox Catalysis

• Published in: Angewandte Chemie (International ed.) Vol. 54; no. 5; pp. 1625 - 1628
• Main Authors: Xuan, Jun, Zeng, Ting-Ting, Feng, Zhu-Jia, Deng, Qiao-Hui, Chen, Jia-Rong, Lu, Liang-Qiu, Xiao, Wen-Jing, Alper, Howard
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 26.01.2015; WILEY‐VCH Verlag; Wiley
• Subjects: Allyl compounds; allylic compounds; Amines; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Derivatives; Merging; Palladium; photochemistry; Physical Sciences; Radicals; Science & Technology; synthetic methods; GOLD; radicals; STRATEGY; BERBERINE; ARYLBORONIC ACIDS; ALLYLIC ACETATES; C-H ARYLATION; NICKEL; photochemistry; allylic compounds; ESTERS; palladium; synthetic methods
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201409999

An unprecedented α‐allylation of amines was achieved by combining palladium catalysis and visible‐light photoredox catalysis. In this dual catalysis process, the catalytic generation of allyl radical from the corresponding π‐allylpalladium intermediate was achieved without additional metal reducing reagents (redox‐neutral). Various allylation products of amines were obtained in high yields through radical cross‐coupling under mild reaction conditions. Moreover, the transformation was applied to the formal synthesis of 8‐oxoprotoberberine derivatives which show potential anticancer properties. Double up: The title reaction was accomplished by merging palladium catalysis and visible‐light photoredox catalysis. The catalytic generation of an allyl radical from the corresponding π‐allylpalladium intermediate was realized without additional metal reducing reagents for the first time. Various α‐allylation products of amines were achieved in high yields by radical cross‐coupling under mild reaction conditions. SET=single‐electron transfer.