title: Oxonitriles: a grignard addition-acylation route to enamides.
abstract: [reaction: see text] Sequential addition of three different Grignard reagents and pivaloyl chloride to 3-oxo-1-cyclohexene-1-carbonitrile installs four new bonds to generate a diverse array of cyclic enamides. Remarkably, formation of the C-magnesiated nitrile intermediate is followed by preferential acylation by pivaloyl chloride rather than consumption by an in situ Grignard reagent. Rapid N-acylation of the C-magnesiated nitrile generates an acyl ketenimine that reacts readily with Grignard reagents or a trialkylzincate, effectively assembling highly substituted, cyclic enamides.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. flemingf@duq.edu
authors.forename: Fraser F
authors.initials: FF
authors.lastname: Fleming
authors.forename: Guoqing
authors.initials: G
authors.lastname: Wei
authors.forename: Zhiyu
authors.initials: Z
authors.lastname: Zhang
authors.forename: Omar W
authors.initials: OW
authors.lastname: Steward
mesh_terms: D000215:Acylation; D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D007202:Indicators and Reagents; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*
chemical_list: D000577:Amides; D007202:Indicators and Reagents; D009570:Nitriles