Nucleophilic Substitution of Hydrogen in Nitroarenes: A New Chapter of Aromatic Chemistry
Nucleophilic Substitution of Hydrogen in Nitroarenes: A New Chapter of Aromatic Chemistry
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硝基芳烃中氢的亲核取代：芳香化学的新篇章
DOI：
10.1002/chin.201147249
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
M. Mąkosza
中科院分区：
文献类型：
--
作者：
M. Mąkosza
简要介绍了硝基芳烃及其他缺电子芳烃中氢的亲核取代反应的基本概念、机理及其在有机合成中的广泛应用。结果表明，亲核试剂与（卤代）硝基芳烃反应的初始过程是一个快速可逆的加成反应--在氢所占据的位置上--形成阴离子σ H加合物，然后通过几种途径转化为氢的亲核取代产物。只有当这些使σ H加合物快速转化为氢的亲核取代产物的途径不存在时，σ H加合物才解离。随后缓慢形成σ X加合物，接着X阴离子离开，导致卤素的常规亲核芳族取代反应，即S N Ar反应。因此，SNAr反应是一个次级IPSO取代反应，而氢的亲核取代反应是一个初级快反应。因此，有必要在教科书和专著的适当章节中引入更正。1引言2氢的氧化亲核取代（ONSH）3氢的替代亲核取代（VNS）4转化σ H加合物的其他方法5氢的亲核取代在有机合成中的应用5.1碳取代基的引入5.2杂原子取代基的引入5.3碳环和杂环的构建6结论讨论
Basic concepts, mechanistic principles and the broad applicationof nucleophilic substitution of hydrogen in nitroarenes and otherelectron-deficient arenes in organic synthesis are presented in aconcise way. It was shown that the initial process between nucleophilesand (halo)nitroarenes is a fast and reversible addition - inpositions occupied by hydrogen - to form anionic σ H adductsthat can then be converted into products of nucleophilic substitutionof hydrogen in a few ways. Only when these pathways for rapid conversionof the σ H adducts into products of nucleophilicsubstitution of hydrogen are not available, do the σ H adductsdissociate. The subsequent slower formation of σ X adducts,followed by departure of X anions, results in the conventional nucleophilicaromatic sub-stitution of halogens, namely the S N Arreaction. Thus the S N Ar reaction is a secondary IPSO substitution, whereas nucleophilic substitutionof hydrogen is a primary fast process. It is therefore necessaryto introduce corrections in appropriate chapters of textbooks andmonographs. 1 Introduction 2 Oxidative Nucleophilic Substitution of Hydrogen (ONSH) 3 Vicarious Nucleophilic Substitution of Hydrogen (VNS) 4 Other Ways of Converting the σ H Adducts 5 Application of Nucleophilic Substitution of Hydrogen in OrganicSynthesis 5.1 Introduction of Carbon Substituents 5.2 Introduction of Heteroatom Substituents 5.3 Construction of Carbo- and Heterocyclic Rings 6 Concluding Discussion