Light‐Driven Enantioselective Synthesis of Pyrroline Derivatives by a Radical/Polar Cascade Reaction

Herein, a light‐driven, atom‐economical process that provides access to enantiomerically enriched substituted chiral 1‐pyrroline derivatives is introduced. The strategy involves the distal functionalization of acyl heterocycles through a hydrogen‐atom transfer (HAT) process and the use of tailor‐made ketimines as reliable electrophilic partners. This transformation is translated into an enantiomerically controlled radical/polar cascade reaction in which water is produced as the sole by‐product and stereoselectivity is dictated by coordination to a chiral‐at‐rhodium catalyst.