Ruthenium-catalysed chemoselective alkylation of nitroarenes with alkanols,Organic Chemistry Frontiers

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Ruthenium-catalysed chemoselective alkylation of nitroarenes with alkanols
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2021-10-13 , DOI: 10.1039/d1qo01269j
Shuang-Shuang Ma _{1,

2} , Rui Sun _{1,

2} , Zi-Heng Zhang _{1,

3} , Zheng-Kun Yu ₄ , Bao-Hua Xu _{1,

2,

4}

Affiliation

The alkylation of nitroarenes with alkanols catalysed by a phosphinesulfonate chelated ruthenium complex [Ru-1] was developed. It exhibits very different reactivity and chemoselectivity depending on acidic–basic conditions. Under either neutral or acidic conditions, nitroarenes were converted to secondary and tertiary anilines, respectively, with secondary and primary alkanols. By contrast, the same catalyst promotes the N-monoalkylation of nitroarenes with primary alkanols under alkaline conditions, while both N-monoalkylation with secondary alkanols and N-dialkylation with primary alkanols are inhibited. Mechanistic studies demonstrated that the novel reactivity under alkaline-free conditions is attributed to the sulfonate ligand-assisted O–H activation of alkanols, thus enabling the reduction of nitroarenes and nucleophilic C–N coupling in a concerted approach. Furthermore, it follows the traditional two-step approach, taking the corresponding imines as the intermediates, under alkaline conditions. Based on such features, diverse secondary and tertiary anilines were obtained directly from nitroarenes using the same catalyst [Ru-1].

中文翻译：

钌催化硝基芳烃与烷醇的化学选择性烷基化

开发了由膦磺酸盐螯合的钌配合物 [ Ru-1 ]催化的硝基芳烃与烷醇的烷基化反应。根据酸碱性条件，它表现出非常不同的反应性和化学选择性。在中性或酸性条件下，硝基芳烃分别转化为仲和叔苯胺，带有仲和伯烷醇。与此相反，同样的催化剂促进Ñ在碱性条件下主链烷醇硝基芳烃的-monoalkylation，同时兼具Ñ -monoalkylation与仲链烷醇和Ñ-与伯烷醇的二烷基化被抑制。机理研究表明，无碱条件下的新反应性归因于磺酸盐配体辅助的烷醇的 O-H 活化，从而能够以协同的方式还原硝基芳烃和亲核 C-N 偶联。此外，它遵循传统的两步法，在碱性条件下以相应的亚胺为中间体。基于这些特征，使用相同的催化剂 [ Ru-1 ]从硝基芳烃中直接获得了不同的仲和叔苯胺。

更新日期：2021-10-30

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