title: Through-bond/through-space anion relay chemistry exploiting vinylepoxides as bifunctional linchpins.
abstract: The development of new bifunctional linchpins that permit the union of diverse building blocks is essential for the synthetic utility of anion relay chemistry (ARC). The design, synthesis, and validation of three vinylepoxide linchpins for through-bond/through-space ARC are now reported. For negative charge migration, this class of bifunctional linchpins employs initial through-bond ARC by an SN 2' reaction, followed by through-space ARC exploiting a 1,4-Brook rearrangement. The trans-disubstituted vinylepoxide linchpin yields a mixture of E/Z isomers, whereas the cis-disubstituted and the trans-trisubstituted vinylepoxide linchpins proceed to deliver three-component adducts with excellent E selectivity.
authors.affiliation: Department of Chemistry, University of Pennsylvania, 231 S. 34thStreet, Philadelphia, PA 19104 (USA).
authors.forename: Ming Z
authors.initials: MZ
authors.lastname: Chen
authors.forename: Osvaldo
authors.initials: O
authors.lastname: Gutierrez
authors.forename: Amos B
authors.initials: AB
authors.lastname: Smith
mesh_terms: D000838:Anions / Q000737:chemistry; D018360:Crystallography, X-Ray; D004852:Epoxy Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D000838:Anions; D004852:Epoxy Compounds
keywords: Brook rearrangement; anion relay chemistry; nucleophilic addition; through-bond interactions; through-space interactions