Reactions of camphor-, and camphene-derived formyl [2.2.1]bicyclic carbinols with Grignard and organolithium reagentsafford the corresponding regio- and stereospecific alkyl/aryl[3.2.1]bicyclic diols. Some of these bicyclic diols have beentreated with lead tetraacetate to provide new chiral cyclopentane derivatives. A plausible mechanism of the ringexpansion-alkylation reaction is proposed.