title: Competitive [2,3]- and [1,2]-oxonium ylide rearrangements. Concerted or stepwise?
abstract: The axial-equatorial conformational isomer distribution of the reactant diazoacetoacetate or its metal carbene intermediate is reflected in Rh(II) catalyzed oxonium ylide forming reactions of 3-(trans-2-arylvinyl)tetrahydropyranone-5-diazoacetoacetates that afford diastereoisomeric products for both the symmetry-allowed [2,3]- and the formally symmetry-forbidden [1,2]-oxonium ylide rearrangements.
authors.affiliation: Department of Biology and Physical Sciences, Marymount University, Arlington, Virginia 22207, USA.
authors.forename: Deana M
authors.initials: DM
authors.lastname: Jaber
authors.forename: Ryan N
authors.initials: RN
authors.lastname: Burgin
authors.forename: Matthew
authors.initials: M
authors.lastname: Helper
authors.forename: Peter Y
authors.initials: PY
authors.lastname: Zavalij
authors.forename: Michael P
authors.initials: MP
authors.lastname: Doyle
mesh_terms: D000090:Acetoacetates / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008697:Methane / Q000031:analogs & derivatives; D008968:Molecular Conformation; D015394:Molecular Structure; D009861:Onium Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000090:Acetoacetates; D009861:Onium Compounds; C030011:carbene; C027727:hydronium ion; D012238:Rhodium; D008697:Methane