Rhodium-Catalyzed Desymmetric Arylation of γ,γ-Disubsituted Cyclohexadienones: Asymmetric Synthesis of Chiral All-Carbon Quaternary Centers

The desymmetric arylation of prochiral cyclohexadienones with ArZnCl in the presence of an (R)-segphos-rhodium catalyst gave high yields of the corresponding cyclohexenones, which contain a chiral arylated carbon center at the beta-position and a chiral all-carbon quaternary center at the gamma-position, with high diastereoand enantioselectivities. This catalytic system was also applied to the arylation of spirocarbocyclic cyclohexadienones and afforded the corresponding cyclohexenones bearing a chiral spiro quaternary carbon with high dr and ee.

Automated summary

This study discovered that the desymmetric arylation of prochiral cyclohexadienones with ArZnCl in the presence of an (R)-segphos-rhodium catalyst can yield cyclohexenones with a chiral arylated carbon center and a chiral all-carbon quaternary center with high selectivity. The catalytic system is also applicable to the arylation of spirocarbocyclic cyclohexadienones, producing cyclohexenones with a chiral spiro quaternary carbon.