A cationic rhodium(I)/BINAP [2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl] complex is capable of catalyzing the [2+2+2] cycloaddition–aromatization of 1,6‐diynes with cyclic enol ethers (2,3‐dihydrofuran and dihydropyran) at room temperature to produce the corresponding aryl alkanol derivatives in good yields. In this process, a conjugated dihydrofuran showed a significantly higher reactivity than a nonconjugated one.

The first asymmetric total synthesis of andranginine (1) via an asymmetric Morita-Baylis-Hillman reaction and a diastereoselective intramolecular Diels-Alder reaction has revealed that natural andranginine (1) isolated from Kopsia arborea existed as a scalemic mixture and contained predominantly the (16R,21S) form rather than the (16S,21R) form.

A cationic rhodium(I)/BINAP complex catalyzes the [2 + 2 + 2] cycloaddition‐aromatization of 1,6‐diynes with cyclic enol ethers.