Asymmetric Photoredox Catalytic Minisci-Type Reactions of α-Bromide Amides

Abstract

An asymmetric photoredox catalytic Minisci-type reaction between α-bromide amides and imine-containing azaarenes has been successfully developed. This catalyst system employs a chiral phosphoric acid alongside 3DPAFIPN as a photosensitizer. The reaction produces a diverse array of valuable amides, featuring azaarene-substituted tertiary carbon stereocenters at the β-position, in high yields (up to 85%) and good to excellent enantioselectivities (up to >99% enantiomeric excess (ee)). Importantly, this work marks the first example of asymmetric radical addition to simple azaarenes utilizing radicals functionalized with electron-withdrawing carbonyl groups, which are conventionally considered unfavorable for such transformations, especially in an enantioselective manner.