title: Reactive intermediates from DMDO oxidation of ynamides. Trapping of a de novo chiral push-pull carbene via cyclopropanation.
abstract: The reaction profile of DMDO oxidations of ynamides is described. This work illustrates the first examples of highly diastereoselective intramolecular cyclopropanations of a push-pull carbene derived from alkyne oxidation. In addition, the ynamide oxidation provides facile access to ketoimides and reveals mechanistic insights into the chemistry of electronically biased oxirenes.
authors.affiliation: Division of Pharmaceutical Sciences and Department of Chemistry, Rennebohm Hall 777 Highland Avenue, University of Wisconsin, Madison, Wisconsin 53705-2222, USA.
authors.forename: Ziyad F
authors.initials: ZF
authors.lastname: Al-Rashid
authors.forename: Richard P
authors.initials: RP
authors.lastname: Hsung
mesh_terms: D003521:Cyclopropanes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D006838:Hydrocarbons / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D010080:Oxazoles / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D003521:Cyclopropanes; D004852:Epoxy Compounds; D006838:Hydrocarbons; D010080:Oxazoles; C030011:carbene; D008697:Methane; C064455:dimethyldioxirane