The synthesis of enantiomerically pure natural products based on an efficient C-C bond formation with chiral synthons via trifluoromethanesulfonates (triflates) is described. Commercially available L- and R-tartrates are used as chiral starting materials and the utility for the enantioselective synthesis of several natural products including (+)-exo-brevicomin, (5R,6S)-(-)-6-acetoxy-5-hexadecanolide, L-factor, lateral root inducing compound, (+)-panaxacol, and (-)-pestalotin is demonstrated.