One-step formation of fused tetracyclic skeletons from cyclohexene-diynes and carbon monoxide through Rh(I)-catalyzed [2 + 2 + 2 + 1] cycloaddition reaction.

Rapid construction of 5-7-6-5 fused tetracyclic carbocycles and heterocycles from cyclohexene-diynes and CO has been achieved in one step through a Rh(i)-catalyzed [2 + 2 + 2 + 1] cycloaddition process.