Abstract
Herein the first enantioselective total synthesis of the C16-nor-fusicoccane diterpenoids (+)-3-ketobrassicicene W and (-)-alterbrassicicene B is described. The strategy evolved from our recent synthesis of (+)-alterbrassicicene C and leveraged the convergent union of two enantioenriched cyclopentene fragments. Substrate controlled stereoselectivity guided the route through hydration, oxidation and reduction steps to deliver (+)-3-ketobrassicicene W which was converted to (-)-alterbrassicicene B upon Lewis acid induced transannular oxa-Michael addition.