title: A Counterion-Directed Approach to the Diels-Alder Paradigm: Cascade Synthesis of Tricyclic Fused Cyclopropanes.
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.
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
authors.forename: Emily
authors.initials: E
authors.lastname: Kiss
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
authors.forename: Craig D
authors.initials: CD
authors.lastname: Campbell
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
authors.forename: Russell W
authors.initials: RW
authors.lastname: Driver
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
authors.forename: John D
authors.initials: JD
authors.lastname: Jolliffe
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
authors.forename: Rosemary
authors.initials: R
authors.lastname: Lang
authors.affiliation: Department of Chemistry, Dnipropetrovsk National University, Dnipropetrovsk, 49010, Ukraine.
authors.forename: Tetiana
authors.initials: T
authors.lastname: Sergeieva
authors.affiliation: Department of Chemistry, Dnipropetrovsk National University, Dnipropetrovsk, 49010, Ukraine.
authors.forename: Sergiy
authors.identifier: 0000-0003-4367-1309
authors.initials: S
authors.lastname: Okovytyy
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK. robert.paton@chem.ox.ac.uk.
authors.forename: Robert S
authors.initials: RS
authors.lastname: Paton
authors.affiliation: Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK. martin.smith@chem.ox.ac.uk.
authors.forename: Martin D
authors.identifier: 0000-0002-8849-488X
authors.initials: MD
authors.lastname: Smith
keywords: cations; cycloadditions; density-functional calculations; diastereoselectivity; heterocycles