Under the conditions of ruthenium catalyzed transfer hydrogenation employing isopropanol as terminal reductant, π-unsaturated compounds (1,3-dienes, allenes, 1,3-enynes and alkynes) reductively couple to aldehydes to furnish products of carbonyl addition. In the absence of isopropanol, π-unsaturated compounds couple directly from the alcohol oxidation level to form identical products of carbonyl addition. Such "alcohol-unsaturate C-C couplings" enable carbonyl allylation, propargylation and vinylation from the alcohol oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. Thus, direct catalytic C-H functionalization of alcohols at the carbinol carbon is achieved.