Radical Cross Coupling and Enantioselective Protonation through Asymmetric Photoredox Catalysis

Authors: Manman Kong, Zhuoxi Wang, Xu Ban, Xiaowei Zhao, Yanli Yin, Junmin Zhang, Zhiyong Jiang

Published: 2024-01-18

DOI: 10.1002/advs.202307773

Source: Full article


Abstract

AbstractAn unprecedented enantioselective protonation reaction enabled by photoredox catalytic radical coupling is developed. Under cooperative dicynopyrazine‐derived chromophore (DPZ) as a photosensitizer and a chiral phosphoric acid catalyst, and Hantzsch ester as a sacrificial reductant, the transformations between α‐substituted enones and cyanoazaarenes or 2‐(chloromethyl)azaaren‐1‐iums can proceed a tandem reduction, radical coupling, and enantioselective protonation process efficiently. Two classes of pharmaceutically important enantioenriched azaarene variants, which contain a synthetically versatile ketone‐substituted tertiary carbon stereocenter at the β‐ or γ‐position of the azaarenes, are synthesized with high yields and ees.