The synthesis of enantiomerically pure (4aS, 5R)-hexahydro-4a, 5-dimethyl-2 (3H)- naphthalenone (−)-1 is described for the first time. The synthesis starts from (R)-3- methylcyclohexanone and involves the preparation of Piers enol lactone 6 in its enantiopure form as the key intermediate. Treatment of (+)-6 with methyl lithium followed by an intramolecular aldol reaction gives the bicyclic enone (−)-1.