Integrative Pericyclic Cascade: An Atom Economic, Multi C−C Bond-Forming Strategy for the Construction of Molecular Complexity

Abstract

An all-pericyclic manifold is developed for the construction of topologically diverse, structurally complex and natural product-like polycyclic chemotypes. The manifold uses readily accessible tertiary propargyl vinyl ethers as substrates and imidazole as a catalyst to form up to two new rings, three new C−C bonds, six stereogenic centers and one transannular oxo-bridge. The manifold is efficient, scalable and instrumentally simple to perform and entails a propargyl Claisen rearrangement–[1,3]H shift, an oxa-6π-electrocyclization, and an intramolecular Diels–Alder reaction.