An unexpected [1,5]-h shift in the synthesis of nitroanilines.
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.
Davies
Ian W
IW
Department of Process Research, Merck & Co., Inc., R800-B263, P.O. Box 2000, Rahway, New Jersey 07065-0900, USA.
Marcoux
Jean-François
JF
Taylor
Jeremy D O
JD
Dormer
Peter G
PG
Deeth
Robert J
RJ
Marcotte
Félix-Antoine
FA
Hughes
David L
DL
Reider
Paul J
PJ