title: An unexpected [1,5]-h shift in the synthesis of nitroanilines.
abstract: Addition of methyl acetoacetate to 2-nitrovinamidinium hexafluorophosphate salts leads to the formation of anilines or phenols in good to excellent yields depending on the alkylamine substituents. Small substituents, e.g., pyrrolidine, lead to the formation of anilines while large substituents, e.g., N,N-diisopropyl, exclusively give phenols. Labeling studies implicate a [1,5]-H shift proceeding with excellent isotopic fidelity.
authors.affiliation: Department of Process Research, Merck & Co., Inc., R800-B263, P.O. Box 2000, Rahway, New Jersey 07065-0900, USA.
authors.forename: Ian W
authors.initials: IW
authors.lastname: Davies
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Marcoux
authors.forename: Jeremy D O
authors.initials: JD
authors.lastname: Taylor
authors.forename: Peter G
authors.initials: PG
authors.lastname: Dormer
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Deeth
authors.forename: Félix-Antoine
authors.initials: FA
authors.lastname: Marcotte
authors.forename: David L
authors.initials: DL
authors.lastname: Hughes
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Reider