title: Unusually reactive and selective carbonyl ylides for three-component cycloaddition reactions.
abstract: Conditions are described for the Rh-catalyzed formation of highly functionalized dihydro- and tetrahydrofuran products via three-component reactions of aldehydes, alpha-alkyl-alpha-diazoesters, and dipolarophiles. The alkyl-substituted carbonyl ylides that are generated in this fashion are highly reactive in cycloaddition reactions and display a scope of reactivity that is much broader than the three-component reactions of carbonyl ylides derived from ethyl diazoacetate or alpha-aryl-alpha-diazoesters. The reactions of alkyl-substituted carbonyl ylides proceed with high regioselectivity and diastereoselectivity that are rationalized in terms of an asynchronous, endo-selective transition state.
authors.affiliation: Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
authors.forename: Andrew
authors.initials: A
authors.lastname: DeAngelis
authors.forename: Michael T
authors.initials: MT
authors.lastname: Taylor
authors.forename: Joseph M
authors.initials: JM
authors.lastname: Fox
mesh_terms: D002255:Carbonic Acid / Q000737:chemistry*; D003500:Cyclization; D015394:Molecular Structure; D017382:Reactive Oxygen Species / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D017382:Reactive Oxygen Species; D002255:Carbonic Acid