Protecting-Group-Free Syntheses of ent-Kaurane Diterpenoids: [3+2+1] Cycloaddition/Cycloalkenylation Approach

The Yu’s Rh-catalyzed [3+2+1] cycloaddition followed by a Pd-mediated 5-endo cycloalkenylation is shown to be a general and powerful approach for efficient construction of the tetracyclic core structure of ent-kaurane diterpenoids. The utility of this strategy was further demonstrated by concise and protecting-group-free total syntheses of ent-1α-hydroxy­kauran-12-one, 12-oxo-9,11-dehydro­kaurene, and 12α-hydroxy-9,11-dehydro­kaurene.