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

5 years ago

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

Jesús Peyrac, Samuel Delgado-Hernández, Fernando García-Tellado, Javier González-Platas, David Tejedor

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. Playing with dominos: An all-pericyclic cascade process transforms propargyl vinyl ethers into eight different polycyclic ring-fused chemotypes incorporating different topologies. The pericyclic manifold creates up to three fused cycles, one transannular-oxo-bridge and six steroigenic centers via the formation of three new C−C bonds.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702667