Axially chiral hydroxy carboxylic acid derivs. were successfully synthesized with high yields and ee values by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed enantioselective [2+2+2] cycloaddn. of diynes with naphthalenepropynoic acid derivs. Axially chiral hydroxy and dihydroxy carboxylic acid derivs., bearing the aryl group at the ortho-position of the alkoxycarbonyl group, were also synthesized with high regio- and enantioselectivity. [on SciFinder(R)]