An unprecedented consecutive SN2'/SN2'' addition of phenol to γ-vinyl MBH carbonate forms a reactive diene intermediate, followed by a dimerization/elimination process to give functionalized exocyclohexenes with excellent chemoselectivity. When using o-hydroxychalcones as pronucleophiles, an SN2'/SN2''/intramolecular Diels-Alder reaction sequence occurs, selectively producing a series of pharmaceutically intriguing tricyclic chromane derivatives with good diastereoselectivity. The good nucleophilicity and fair nucleofugicity exhibited by phenoxy anion play a pivotal role in the SN2'' addition step.