One-point binding chiral ruthenium Lewis acids incorporating the C₂-symmetric electron-poor bidentate phosphinite ligand BIPHOP-F and a Cp or an indenyl ‘roof’ can efficiently catalyze asymmetric intramolecular Diels–Alder reactions of trienes to form bicyclic adducts with good to excellent asymmetric induction. This reaction forms the key step in a total synthesis of ent-ledol in 96% ee. The synthesis also helps to clarify the stereochemical assignment of ledol and inconsistencies in the measured optical rotation.