亚磷酰胺及其同类物的取代反应机理,Journal of Physical Organic Chemistry

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亚磷酰胺及其同类物的取代反应机理
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 17 November 2003 , DOI: 10.1002/poc.681
Erkki Nurminen , Harri Lönnberg

综述了三价磷化合物亲核取代的机理研究，重点是亚磷酰胺的反应。这些化合物对羟基的反应性例如在寡核苷酸的现代自动固相支持物合成的偶联步骤中被利用。对寡核苷酸作为反义策略药物的大规模合成的兴趣日益浓厚，这增加了对相关机理研究的需求，这在过去几年中大大提高了我们对亚磷酰胺醇解反应的理解。该综述还涵盖了作为该反应产物而形成的亚磷酸酯，以及用作其中间体的亚磷酸卤代石，偶氮基亚膦酸酯和P（III）偶氮代锂盐。包括亚磷酰胺与吡咯和碳糖酸的反应机理，以及卤化和转酰胺基反应的机理。文献中发表的用于P（III）化合物取代反应的替代反应机制涵盖了从解离途径到协同途径和缔合途径的多种途径，同时还提出了不同类型的活化方法。已显示亚磷酰胺与醇的反应既受亲核催化又受酸催化，并且很可能以协同的解离机理进行。还讨论了这些结论对开发亚磷酰胺合成方法的亚磷酰胺方法的影响。版权所有©2003 John Wiley＆Sons，Ltd. 文献中发表的用于P（III）化合物取代反应的替代反应机制范围从解离途径，协同途径和缔合途径不等，但已提出了不同类型的活化方法。已显示亚磷酰胺与醇的反应既受亲核催化又受酸催化，并且很可能以协同的解离机理进行。还讨论了这些结论对开发亚磷酰胺合成方法的亚磷酰胺方法的影响。版权所有©2003 John Wiley＆Sons，Ltd. 文献中发表的用于P（III）化合物取代反应的替代反应机制涵盖了从解离途径到协同途径和缔合途径的多种途径，同时还提出了不同类型的活化方法。已显示亚磷酰胺与醇的反应既受亲核催化又受酸催化，并且很可能以协同的解离机理进行。还讨论了这些结论对开发亚磷酰胺合成方法的亚磷酰胺方法的影响。版权所有©2003 John Wiley＆Sons，Ltd. 已显示亚磷酰胺与醇的反应既受亲核催化又受酸催化，并且很可能以协同的解离机理进行。还讨论了这些结论对开发亚磷酰胺合成方法的亚磷酰胺方法的影响。版权所有©2003 John Wiley＆Sons，Ltd. 已显示亚磷酰胺与醇的反应既受亲核催化又受酸催化，并且很可能以协同的解离机理进行。还讨论了这些结论对开发亚磷酰胺合成方法的亚磷酰胺方法的影响。版权所有©2003 John Wiley＆Sons，Ltd.

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Mechanisms of the substitution reactions of phosphoramidites and their congeners

Mechanistic research on the nucleophilic substitution of trivalent phosphorus compounds is reviewed with emphasis on the reactions of phosphoramidites. The reactivity of these compounds towards hydroxyl groups is utilized, for instance, in the coupling step of the modern automated solid-support synthesis of oligonucleotides. Growing interest in the large-scale synthesis of oligonucleotides as antisense-strategy drugs has increased the demand for relevant mechanistic research that has considerably improved our understanding of phosphoramidite alcoholysis reaction during the last few years. The review also covers phosphites that are formed as products of this reaction and also phosphorohalidites, azolyl phosphonites and P(III) azolidites that serve as its intermediates. Mechanisms of reactions of phosphoramidites with azoles and carbozylic acids are included together with those of halogenation and transamidation. Alternative reaction mechanisms published in the literature for substitution reactions of P(III) compounds range from dissociative to concerted and associative pathways while different types of activation have been suggested. Reactions of phosphoramidites with alcohols have been shown to be subject to both nucleophilic and acid catalysis and most likely proceed with a concerted mechanism of dissociative character. The consequences of these conclusions for the development of the phosphoramidite approach of oligonucleotide synthesis are also discussed. Copyright © 2003 John Wiley & Sons, Ltd.

更新日期：2017-01-31

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