When benzylic and allylic alcohols were treated with enolacetate in the presence of a catalytic amount of a rhenium complex, ReBr(CO)5, the carbon-carbon bond formation of the alcohols and enolacetate smoothly proceeded to give the corresponding ketones and aldehyde in moderate to good yields. For the reaction of allylic alcohols, γ,δ-unsaturated carbonylcompounds were obtained in good yields. When