The intramolecular Pauson-Khand reaction of enol and ynol ethers of Oppolzer's camphor-derived neopentyloxy alcohols is described. Bicyclic products are obtained in yields of up to 65% and with diastereoselectivities as high as 94:6 under very mild reaction conditions. The absolute configurations of the major stereoisomers obtained when (1 R, 2 S, 3 R, 4 S)-3-neopentyloxy-1,7,7-trimethylbicyclo- [2.2.1]heptan-2-ol is used as a chiral auxiliary are rationalized on the basis of the theoretically predicted preferential conformations of model precursors. A simple procedure for obtaining auxiliary-free, enantiopure bicyclic α-methoxyenones is also presented.