Enantio- and Diastereoselective Synthesis of Functionalized Carbocycles by Cu-Catalyzed Borylative Cyclization of Alkynes with Ketones

A single-pot Cu-catalyzed enantio- and diaster-eoselective tandem hydroboration/borylative cyclization of alkynes with ketones for the synthesis of carbocycles is reported. The reaction proceeds via desymmetrization and generates four contiguous stereocenters, including an all-carbon quaternary center. The method provides rapid access to [6,5]- and [5,5]-bicycles and cyclopentane products. Catalyst-controlled diastereoselectivity by selection of bisphosphine ligand is noted. Utility of the products is demonstrated by site- and chemoselective transformations that afford valuable alkenyl and allyl organoborons.