On the mechanism of the dimethyldioxirane oxidation of sigma(H) adducts (Meisenheimer complexes) generated from nitroarenes and carbanions
The mechanism of the novel dimethyldioxirane (DMD) oxidation of sigma(H) adducts (Meisenheimer complexes) generated from nitroarenes and carbanions was elucidated. The proposed mechanism, which is akin to that of the oxidative Nef reaction, is supported by the isolation of the cyclohexadienone intermediate and the lack of a primary kinetic isotopic effect. Protic solvents (H(2)O, MeOH) enhance the reactivity of DMD through intermolecular hydrogen bonding.
Adam
W
Institute of Organic Chemistry, University of Wurzburg, Am Hubland, D-97074 Wurzburg, Germany, and Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.
Makosza
M
Zhao
CG
Surowiec
M