title: Rhodium-catalyzed enantioselective vinylogous addition of enol ethers to vinyldiazoacetates.
abstract: A highly asymmetric vinylogous addition of acyclic silyl enol ethers to siloxyvinyldiazoacetate is described. The reaction features a diastereoselective 1,4-siloxy group migration event. Products are obtained in up to 97% ee. When more sterically crowded silyl enol ethers are employed, an enantioselective formal [3+2] cycloaddition becomes the dominant reaction pathway. Control experiments reveal the (Z)-olefin geometry to be critical for high levels of enantiocontrol.
authors.affiliation: Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
authors.forename: Austin G
authors.initials: AG
authors.lastname: Smith
authors.forename: Huw M L
authors.initials: HM
authors.lastname: Davies
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D004987:Ethers / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000475:Alkenes; D001391:Azo Compounds; D004987:Ethers; D012238:Rhodium