Rhodium-catalyzed asymmetric one-pot transesterification and [2 + 2 + 2] cycloaddition leading to enantioenriched 3,3-disubstituted phthalides.

[structure: see text]. We have developed a cationic rhodium(I)/Solphos complex-catalyzed asymmetric one-pot transesterification and [2 + 2 + 2] cycloaddition of 1,6-diyne esters with tertiary propargylic alcohols leading to enantioenriched tricyclic 3,3-disubstituted phthalides. The present method represents a versatile new route to the synthesis of enantioenriched tricyclic 3,3-disubstituted phthalides in view of the easy access to both coupling partners.