{"title":"Nucleophilic substitution at phosphorus: stereochemistry and mechanisms","authors":"Oleg I. Kolodiazhnyi, Anastasy Kolodiazhna","doi":"10.1016/j.tetasy.2017.10.022","DOIUrl":null,"url":null,"abstract":"<div><p><span><span>This review is devoted to the stereochemistry of </span>nucleophilic substitution reactions<span><span> at phosphorus. The study of the reactions of phosphoryl group transfer is important for biological and molecular </span>chemistry. The stereochemistry and mechanisms of S</span></span><sub>N</sub>1(P) monomolecular and S<sub>N</sub><span>2(P) bimolecular nucleophilic substitution reactions of organophosphorus compounds are discussed. It has been shown that hydrolysis of many natural phosphates proceeds according to the monomolecular S</span><sub>N</sub>1(P) mechanism via the formation of metaphosphate intermediate (PO<sub>3</sub><sup>−</sup>). S<sub>N</sub><span>2(P) nucleophilic substitution at chiral trivalent or pentavalent phosphorus compounds proceeds via the formation of penta-coordinated transition state or pentacoordinate intermediate.</span></p></div>","PeriodicalId":22237,"journal":{"name":"Tetrahedron, asymmetry","volume":"28 12","pages":"Pages 1651-1674"},"PeriodicalIF":0.0000,"publicationDate":"2017-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.tetasy.2017.10.022","citationCount":"37","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Tetrahedron, asymmetry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0957416617304603","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"Chemistry","Score":null,"Total":0}
引用次数: 37
Abstract
This review is devoted to the stereochemistry of nucleophilic substitution reactions at phosphorus. The study of the reactions of phosphoryl group transfer is important for biological and molecular chemistry. The stereochemistry and mechanisms of SN1(P) monomolecular and SN2(P) bimolecular nucleophilic substitution reactions of organophosphorus compounds are discussed. It has been shown that hydrolysis of many natural phosphates proceeds according to the monomolecular SN1(P) mechanism via the formation of metaphosphate intermediate (PO3−). SN2(P) nucleophilic substitution at chiral trivalent or pentavalent phosphorus compounds proceeds via the formation of penta-coordinated transition state or pentacoordinate intermediate.
期刊介绍：
Cessation. Tetrahedron: Asymmetry presents experimental or theoretical research results of outstanding significance and timeliness on asymmetry in organic, inorganic, organometallic and physical chemistry, as well as its application to related disciplines, especially bio-organic chemistry.
The journal publishes critical reviews, original research articles and preliminary communications dealing with all aspects of the chemical, physical and theoretical properties of non-racemic organic and inorganic materials and processes. Topics relevant to the journal include: the physico-chemical and biological properties of enantiomers; strategies and methodologies of asymmetric synthesis; resolution; chirality recognition and enhancement; analytical techniques for assessing enantiomeric purity and the unambiguous determination of absolute configuration; and molecular graphics and modelling methods for interpreting and predicting asymmetric phenomena. Papers describing the synthesis or properties of non-racemic molecules will be required to include a separate statement in the form of a Stereochemistry Abstract, for publication in the same issue, of the criteria used for the assignment of configuration and enantiomeric purity.
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