Ruthenium-BINAP Catalyzed Alcohol C–H tert-Prenylation via 1,3-Enyne Transfer Hydrogenation: Beyond Stoichiometric Carbanions in Enantioselective Carbonyl Propargylation

The chiral ruthenium complex formed in situ from (TFA)2Ru­(CO)­(PPh3)2 and (R)-BINAP is found to catalyze the enantioselective C–C coupling of diverse primary alcohols with the 1,3-enyne, TMSCCC­(Me)CH2, to form secondary homopropargyl alcohols bearing gem-dimethyl groups. All reagents for this byproduct-free coupling are inexpensive and commercially available, making this protocol a practical alternative to stoichiometric carbanions in enantioselective carbonyl reverse prenylation.