Substrate encapsulation: An efficient strategy for the RCM synthesis of unsaturated ε-lactones

(Chemical Equation Presented) A facile substrate-encapsulated RCM-based synthesis of 7-membered lactones is reported. Coordination of the α,ω-dienyl ester precursor to the bulky Lewis acid (LA) aluminum tris(2,6-diphenylphenoxide) (ATPH) provides a protective extended steric pocket to the olefin moieties, thereby favoring intramolecular RCM over intermolecular ADMET oligomerization. The LA-encapsulated esters undergo ring-closure in the presence of Ru-based olefin metathesis catalysts to give previously difficult-to-access 7-membered β,γ- and γ,δ-unsaturated lactones in good yields.