title: Experimental and theoretical study of the 2-alkoxyethylidene rearrangement.
abstract: The rearrangement of 2-ethoxyethylidene, generated photochemically from a nonnitrogenous precursor, leads to ethyl vinyl ether. Although this product could result, in principle, from a 1,2-hydrogen shift and/or a 1,2-ethoxy shift in the carbene, a deuterium labeling study indicates an essentially exclusive preference for hydrogen migration. The experimental results are in agreement with CCSD and W1BD calculations for the simpler 2-methoxyethylidene system that show a prohibitively large barrier for the methoxy shift and a negligible barrier for the hydride shift.
authors.affiliation: Department of Chemistry, Colby College, Waterville, Maine 04901, USA.
authors.forename: Kimberly S
authors.initials: KS
authors.lastname: Graves
authors.forename: Dasan M
authors.initials: DM
authors.lastname: Thamattoor
authors.forename: Paul R
authors.initials: PR
authors.lastname: Rablen