62267-02-1Relevant articles and documents
Nitrone/Imine Selectivity Switch in Base-Catalysed Reaction of Aryl Acetic Acid Esters with Nitrosoarenes: Joint Experimental and Computational Study
Volpe, Chiara,Meninno, Sara,Roselli, Angelo,Mancinelli, Michele,Mazzanti, Andrea,Lattanzi, Alessandra
supporting information, p. 5457 - 5466 (2020/10/12)
Herein we report a mild and diastereoselective access to ketonitrones by reacting easily available aryl acetic acid esters and other active methylene compounds, with nitrosoarenes under catalytic loading of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) at room temperature. Depending on the substitution pattern and nature of the aryl moiety, a switch toward the formation of imines can be observed. The mechanistic framework is put to scrutiny by experimental and theoretical studies, pointing to the formation of a nitroso aldol intermediate, whose fate toward one of the competing pathways, namely hydride transfer or elimination, would depend upon the NOH/CHα relative acidities. (Figure presented.).
Mechanism of Acid-Catalyzed Hydrolysis of Phenylketene O,O and O,S Acetals
Okuyama, Tadashi,Kawao, Shoji,Fueno, Takayuki
, p. 4372 - 4375 (2007/10/02)
The hydrolysis of a phenylketene O,O acetal (1,1-dimethoxy-2-phenylethene, 1) and an O,S acetal have been studied kinetically at 30 deg C.The observed catalysis by general acids, the deuterium solvent isotope effects (kH2O/kD2O = 5.5 with 1), and the lack of nucleophilic acceleration by added 2-mercaptoethanol are in accord with a mechanism involving rate-determining protonation of the double bond.The nonlinear dependence of rate on formate buffer concentration was observed in the hydrolysis of 2, but it does not seem to be ascribable to a possible change in the rate-determining step in contrast to the previous suggestion.