Performing catalytic enantioselective carbon-carbon bond forming reactions, especially for the synthesis of tertiary carbinols, is one of the most challenging goals in modern asymmetric synthesis. Herein, we report an efficient enantioselective catalytic approach for the 1,2-addition of arylboronic acids to trifluoromethyl ketones affording tertiary trifluoromethyl-substituted alcohols with high yields and good enantioselectivities. The reported process uses as a catalyst precursor the shelf stable sulfinamido-olefin ligand 1, "sulfolefin", obtained on a multigram scale and in one step from a sugar derived sulfinate ester.