Brønsted Base Catalyzed One‐Pot Synthesis of Stereodefined Six‐Member Carbocycles Featuring Transient Trienolates and a Key Intramolecular 1,6‐Addition

A catalyst‐driven one‐pot reaction sequence is developed for the enantio‐ and diastereoselective synthesis of tetrasubstituted cyclohexenes from simple unsaturated ketones or thioesters. The method involves a tertiary amine/squaramide‐catalyzed α‐selective addition of transiently generated trienolates to nitroolefins, subsequent base‐catalyzed double bond isomerization, and an intramolecular (vinylogous) 1,6‐addition reaction, a rare key carbocyclization step that proceeded with essentially perfect stereocontrol.