{"title":"Conformationally restricted donors for stereoselective glycosylation.","authors":"Kaname Sasaki, Nanako Uesaki","doi":"10.1016/bs.accb.2022.10.005","DOIUrl":null,"url":null,"abstract":"<p><p>In nucleophilic reactions using sugars as electrophiles, i.e., glycosyl donors, their conformation affects the generation rate or stability of the glycosyl cation intermediates and determines at which side of the S<sub>N</sub>2-S<sub>N</sub>1 borderline and at what rate the reaction occurs. In addition, changes in the conformation create the steric or stereoelectronic effects of the substituents, which also change the reaction rate and stereoselectivity. Bulky silyl protecting groups, uronic acid esters, and transannular structures have been utilized to change the conformation. Consequently, reactions with unique reactivities and stereoselectivities have been developed. In this chapter, a discussion of the reaction mechanisms relating stereoselectivity to conformation is provided.</p>","PeriodicalId":7215,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"82 ","pages":"107-155"},"PeriodicalIF":0.0000,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advances in carbohydrate chemistry and biochemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/bs.accb.2022.10.005","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"Chemistry","Score":null,"Total":0}
引用次数: 0
Abstract
In nucleophilic reactions using sugars as electrophiles, i.e., glycosyl donors, their conformation affects the generation rate or stability of the glycosyl cation intermediates and determines at which side of the SN2-SN1 borderline and at what rate the reaction occurs. In addition, changes in the conformation create the steric or stereoelectronic effects of the substituents, which also change the reaction rate and stereoselectivity. Bulky silyl protecting groups, uronic acid esters, and transannular structures have been utilized to change the conformation. Consequently, reactions with unique reactivities and stereoselectivities have been developed. In this chapter, a discussion of the reaction mechanisms relating stereoselectivity to conformation is provided.
期刊介绍：
Advances in Carbohydrate Chemistry and Biochemistry has provided, since its inception in 1945, critical and informative articles written by research specialists that integrate the industrial, analytical, and technological aspects of biochemistry, organic chemistry, and instrumentation methodology to the study of carbohydrates. Its articles present a definitive interpretation of the current status and future trends in carbohydrate chemistry and biochemistry.
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