214330-01-5Relevant academic research and scientific papers
A Novel NO2/OH Exchange in α-Nitro Ketones: A Mechanistic Investigation
Yurdakul, Aycil,Gurtner, Christian,Jung, Elena-Silvia,Lorenzi-Riatsch, Annalaura,Linden, Anthony,Guggisberg, Armin,Bienz, Stefan,Hesse, Manfred
, p. 1373 - 1392 (1998)
The reaction of α-nitro ketones to the corresponding α-hydroxy ketones under basic aqueous conditions, a novel transformation, was studied. The investigation revealed that the reaction is only possible with α-nitro ketones that are CH-acidic in the α′-position and readily deprotonated under the reaction conditions. The NO2/OH exchange was established to proceed with retention of configuration at the stereogenic center, and labeling experiments have shown that the OH O-atom originates, to a great extent, from the solvent. In particular, the stereochemical course of the reaction and the incorporation of external nucleophiles led us to propose a mechanism that involves neighboring-group participation. The product formation is explained by a double SN2 reaction, which proceeds via a favorsii-like cyclopropanone intermediate.
