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

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.This research was supported by the Spanish Ministerio de Economía y Competitividad and ERDF (CTQ2015‐63894‐P).Peer reviewe