Highly diastereo- and enantioselective construction of both central and axial chiralities by Rh-catalyzed [2 + 2 + 2] cycloaddition.

The cationic Rh-SEGPHOS complex catalyzed an intermolecular [2 + 2 + 2] cycloaddition of enynes, possessing an ortho-substituted aryl group on their alkyne terminus, with acetylenedicarboxylates. Bicyclic cyclohexa-1,3-dienes with both central and axial chiralities were obtained in extremely highly diastereo- and enantioselective manner.