The development and application of stereoselective and site-selective catalytic methods that directly convert lower alcohols to higher alcohols are described. These processes merge the characteristics of transfer hydrogenation and carbonyl addition, exploiting alcohols and π-unsaturated reactants as redox pairs, which upon hydrogen transfer generate transient carbonyl-organometal pairs en route to products of C-C coupling. Unlike classical carbonyl additions, stoichiometric organometallic reagents and discrete alcohol-to-carbonyl redox reactions are not required. Additionally, due to a kinetic preference for primary alcohol dehydrogenation, the site-selective modification of glycols and higher polyols is possible, streamlining or eliminating use of protecting groups. The total syntheses of several iconic type I polyketide natural products were undertaken using these methods. In each case, the target compounds were prepared in significantly fewer steps than previously achieved.