Russian Chemical Bulletin, International Edition, Vol. 61, No. 7, pp. 1321—1341, July, 2012 1321 Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1307—1326, July, 2012. 1066-5285/12/6107-1321 © 2012 Springer Science+Business Media, Inc. Reactions of oxidative nucleophilic substitution of hydrogen in nitroarenes* A. V. Gulevskaya and I. N. Tyaglivaya Southern Federal University, Chemical Department, 7 ul. Zorge, 344090 Rostov-on-Don, Russian Federation. Fax: +7 (863) 297 5151. E-mail: agulevskaya@sfedu.ru The review summarizes information on the reactions of oxidative nucleophilic substitution of hydrogen in nitro derivatives of carboaromatic substrates with N-, C-, O-, and P-nucleo- philes. Key words: oxidative nucleophilic substitution of hydrogen, nitroarenes. Introduction One of the fundamental properties of aromatic com- pounds is their tendency to the substitution reactions. It is generally accepted that electrophilic substitution is the more characteristic of them, though the easiness of this substitution directly depends on the nucleophilic character of compounds, which is defined by the presence of activat- ing electron-releasing substituents in the aromatic ring. The majority of electrophilic substitution reactions proceed as substitution of hydrogen (S E H ). The electrophilic pro- cess, in which a substituent other than hydrogen is ex- changed, are rare and are called ipso-substitution (S E ipso ). Nucleophilic aromatic substitution is no less impor- tant and no less common type of reactions of aromatic compounds, which is characteristic of electrophilic are- nes. Electrophilic character of the aromatic ring can be due to the presence of electron-withdrawing substituents (in particular, a nitro group), ring heteroatoms, -com- plexation with transition metals, or other structural fea- tures. According to the modern conceptions, 1—11 the reac- tions of electrophilic arenes with nucleophiles follow a two- step mechanism of addition—elimination (Scheme 1). In the first step, formation of intermediates of two types is possible: the  X -adducts (Meisenheimer complexes) or the  H -adducts (Servis complexes). As a rule, an addition of nucleophile to unsubstituted carbon is more rapid process than a nucleophilic ipso-attack. Even if a good leaving group is present in the ring, a rapid and reversible forma- tion of  H -adducts as kinetically controlled products al- * Based on the Materials of the International Congress on Organic Chemistry dedicated to the 150th anniversary of the Butlerov´s Theory of Chemical Structure of Organic Compounds (September 19—23, 2011, Kazan, Russia). Scheme 1 EWG is the electron-withdrawing group (NO 2 , aza group, M n+ , etc.); Nu is the nucleophile, X is the good leaving group (Hal, NO 2 , etc.)