Unusually reactive and selective carbonyl ylides for three-component cycloaddition reactions.
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.
DeAngelis
Andrew
A
Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
Taylor
Michael T
MT
Fox
Joseph M
JM
D002255:Carbonic Acid / Q000737:chemistry*; D003500:Cyclization; D015394:Molecular Structure; D017382:Reactive Oxygen Species / Q000737:chemistry; D013237:Stereoisomerism
D017382:Reactive Oxygen Species; D002255:Carbonic Acid