4,4-Dimethyl-2-(3-chloro-2-methyl-1-propenyl)-2-oxazoline has been synthesized and deprotonated with LDA in THF to give the corresponding lithiated species, which has been found to react are -gioselectively with NH 4 Cl and alkyl halides, and g-regioselectively with carbonyl compounds to afford a-protonated (or a-alkyl-substituted) regioisomers and vinyl epoxides, respectively. The Z diaster-eoselectivity of both the protonation and the alkylation reactions was usually found to increase with the temperature. Ab initio calculations, performed on both the naked lithium salt and the corresponding solvated form, support the observed regioselectivity.