title: Exploring the original proposed biosynthesis of (+)-symbioimine: remote exocyclic stereocontrol in a type I IMDA reaction.
abstract: The originally proposed biosynthesis of (+)-symbioimine was explored, resulting in the successful intramolecular Diels-Alder (IMDA) cyclization of an appropriate (E,E,E)-1,7,9-decatrien-3-one. In contrast to the originally proposed biosynthesis, the IMDA reaction appears to proceed via an endo transition state. Remarkably, a single exocyclic stereogenic center effectively controls the pi-facial selectivity affording a highly diastereoselective cycloaddition.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA.
authors.forename: Jason P
authors.initials: JP
authors.lastname: Burke
authors.forename: Michal
authors.initials: M
authors.lastname: Sabat
authors.forename: Diana A
authors.initials: DA
authors.lastname: Iovan
authors.forename: William H
authors.initials: WH
authors.lastname: Myers
authors.forename: Jason J
authors.initials: JJ
authors.lastname: Chruma
mesh_terms: D000475:Alkenes / Q000737:chemistry; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D007659:Ketones / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000475:Alkenes; D006575:Heterocyclic Compounds, 3-Ring; D007659:Ketones; C505668:symbioimine