Enantiocontrolled Synthesis of Trialkyl-Substituted Stereogenic Carbons. A General Route to cis-3,5-Dialkyl γ-Lactones

[reaction: see text] Lewis acid treatment of tertiary Co2(CO)6-propargylic alcohols having a stereochemically defined benzyloxy group at the gamma-benzyl position yielded after cobalt demetalation sec-dialkyl bishomopropargylic alcohols in good yields. The reaction is highly stereoselective and predictable, providing pure stereoisomers. The use of benzyl-alpha,alpha'-d2 ethers permitted the stereoselective d-labeling of methines and methylenes. Very simple chemical manipulations provided a general methodology to obtain the enantiomers of 3,5-dialkyl-gamma-lactones.