Natural (E)-(7R, 11R)-Phytol (1), a component of the chlorophyll molecule, vitamin K1 (2) and other natural compounds, was synthesized in enantiomerically and diastereomerically pure form by Li2CuCl4-induced coupling of two C10-units (8, 12). Both these units were prepared from geraniol (3) via enzymatic enantioselective hydrogenation of activated double bonds.