Enantioselective nickel-catalyzed arylative intramolecular 1,4-allylations

The enantioselective nickel-catalyzed desymmetrization of allenyl cyclohexa-2,5-dienones by reaction with arylboronic acids is described. Nickel-catalyzed arylation of the allene gives allylnickel species, which undergo cyclization by 1,4-allylation to produce hexahydroindol-5-ones and hexahydrobenzofuran-5-ones with three contiguous stereocenters in high diastereo- and enantioselectivities. The enantioselective desymmetrization of allenyl cyclohexa-2,5-dienones by nickel-catalyzed arylative intramolecular 1,4-allylations is described.