874-52-2Relevant articles and documents
KINETIC SOLVENT DEUTERIUM ISOTOPE EFFECT ON THE OXYGENATION OF N,N-DIMETHYLANILINE WITH THE PIG LIVER MICROSOMAL FAD-CONTAINING MONOOXYGENASE
Fujimori, Ken,Yaguchi, Masafumi,Mikami, Akihiro,Matsuura, Takaharu,Furukawa, Naomichi,et al.
, p. 1179 - 1182 (1986)
Both the maximum velocity and the Michaelis constant of the oxygenation of N,N-dimethylaniline with the pig liver microsomal FAD-containing monooxygenase (EC 1.14.13.8) to N,N-dimethylaniline N-oxide appear 1.7 folds greater in aqeous buffer solution of pH 7.4 than those in deuterium oxide buffer solution of pD 7.4.
SO2F2-mediated oxidation of primary and tertiary amines with 30% aqueous H2O2 solution
Liao, Xudong,Zhou, Yi,Ai, Chengmei,Ye, Cuijiao,Chen, Guanghui,Yan, Zhaohua,Lin, Sen
supporting information, (2021/11/01)
A highly efficient and selective oxidation of primary and tertiary amines employing SO2F2/H2O2/base system was described. Anilines were converted to the corresponding azoxybenzenes, while primary benzylamines were transformed into nitriles and secondary benzylamines were rearranged to amides. For tertiary amine substrates quinolines, isoquinolines and pyridines, their oxidation products were the corresponding N-oxides. The reaction conditions are very mild and just involve SO2F2, amines, 30% aqueous H2O2 solution, and inorganic base at room temperature. One unique advantage is that this oxidation system is just composed of inexpensive inorganic compounds without the use of any metal and organic compounds.
Dimethylanilinic N-Oxides and Their Oxygen Surrogacy Role in the Formation of a Putative High-Valent Copper-Oxygen Species
Diaz, Daniel E.,Bhadra, Mayukh,Karlin, Kenneth D.
, p. 13746 - 13750 (2019/10/14)
The reaction of p-cyano-N,N-dimethylaniline N-oxide, an O-atom donor, with different copper(I) complexes (at room temperature and in acetone) indicates the formation via O-atom transfer of a high-valent copper oxyl species, CuII-O?, a putative key intermediate in the catalytic cycle of copper-containing monooxygenases. The formation of p-cyano-N-hydroxymethyl-N-methylaniline and p-cyano-N-methylaniline as the main products of the reaction highlight the capability of this species to hydroxylate strong C-H bonds (bond dissociation energy ～90 kcal/mol). A plausible mechanism for the reactivity of this catalytic system is proposed.
Oxido-alcoholato/thiolato-molybdenum(VI) complexes with a dithiolene ligand generated by oxygen atom transfer to the molybdenum(IV) complexes
Sugimoto, Hideki,Sato, Masanori,Asano, Kaoru,Suzuki, Takeyuki,Ogura, Takashi,Itoh, Shinobu
, p. 42 - 48 (2018/10/20)
Oxido-alcoholato- and oxido-thiolato-molybdenum(VI) complexes bearing two ene-1,2-dithiolate ligands (cyclohexene-1,2-dithiolate) are prepared as synthetic models of molybdenum(VI) reaction centers of dimethyl sulfoxide reductase family of molybdenum enzymes. These complexes are prepared by oxygen atom transfer from tertiary amine N-oxide (trimethylamine N-oxide and N,N-dimethylaniline N-oxide) to the five-coordinate alcoholato- and thiolato-molybdenum(IV) complexes, and are characterized by UV–vis, cold-spray-ionization mass, resonance Raman, and 1H NMR spectroscopies. The oxygen atom transfer reactions are studied kinetically at a low temperature (?40 °C) to demonstrate that the reactivity of the thiolato-molybdenum(IV) complex is higher than that of alcoholato-molybdenum(IV) complex by about 7 times, and that the oxygen atom transfer reactivity increases with increasing the electron withdrawing ability of the p-substituent of N,N-dimethylaniline N-oxide derivatives. Mechanistic details are discussed based on the reactivity studies.
