A Counterion-Directed Approach to the Diels-Alder Paradigm: Cascade Synthesis of Tricyclic Fused Cyclopropanes

Emily Kiss; Craig D Campbell; Russell W Driver; John D Jolliffe; Rosemary Lang; Tetiana Sergeieva; Sergiy Okovytyy; Robert S Paton; Martin D Smith

doi:10.1002/anie.201608534

A Counterion-Directed Approach to the Diels-Alder Paradigm: Cascade Synthesis of Tricyclic Fused Cyclopropanes

Angew Chem Int Ed Engl. 2016 Oct 24;55(44):13813-13817. doi: 10.1002/anie.201608534. Epub 2016 Oct 7.

Authors

Emily Kiss¹, Craig D Campbell¹, Russell W Driver¹, John D Jolliffe¹, Rosemary Lang¹, Tetiana Sergeieva², Sergiy Okovytyy², Robert S Paton³, Martin D Smith⁴

Affiliations

¹ Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
² Department of Chemistry, Dnipropetrovsk National University, Dnipropetrovsk, 49010, Ukraine.
³ Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK. robert.paton@chem.ox.ac.uk.
⁴ Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK. martin.smith@chem.ox.ac.uk.

Abstract

An approach to the intramolecular Diels-Alder reaction has led to a cascade synthesis of complex carbocycles composed of three fused rings and up to five stereocenters with complete stereocontrol. Computational analysis reveals that the reaction proceeds by a Michael/Michael/cyclopropanation/epimerization cascade in which size and coordination of the counterion is key.

Keywords: cations; cycloadditions; density-functional calculations; diastereoselectivity; heterocycles.

Publication types

Research Support, Non-U.S. Gov't