title: Synthesis of silyloxy dienes by silylene transfer to divinyl ketones: application to the asymmetric synthesis of substituted cyclohexanes.
abstract: Silver-catalyzed silylene transfer to divinyl ketones provided 2-silyloxy-1,3-dienes with control of stereochemistry and regioselectivity. The products participated in Diels-Alder reactions with electron-deficient alkenes and imines to form six-membered-ring products diastereoselectively. Cycloaddition reactions with alkenes bearing chiral auxiliaries provided access to chiral, nonracemic cyclohexenes. The methodology, therefore, represents a synthesis of diastereomerically and enantiomerically pure products in a single flask. The highly substituted cyclohexene products could be functionalized stereoselectively to provide cyclohexanols after oxidation of the carbon-silicon bond.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
authors.forename: Christian C
authors.initials: CC
authors.lastname: Ventocilla
authors.forename: K A
authors.initials: KA
authors.lastname: Woerpel
mesh_terms: D002384:Catalysis; D003510:Cyclohexanes / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D003510:Cyclohexanes; D017646:Organosilicon Compounds; D014753:Vinyl Compounds