Enantioselective total synthesis of (+)-asteriscanolide via Rh(i)-catalyzed [(5+2)+1] reaction

The total synthesis of (+)-asteriscanolide starting from two commercially available materials has been accomplished in 19 steps with a 3.8% overall yield. The key reaction is a chiral ene-vinylcyclopropane substrate induced Rh(I)-catalyzed [(5+2)+1] cycloaddition that efficiently constructs the [6.3.0] carbocyclic core with complete asymmetric induction.