DC Field | Value | Language |
---|---|---|
dc.contributor.author | Wang, Sibin | ko |
dc.contributor.author | Zhelavskyi, Oleksii | ko |
dc.contributor.author | Lee, Jeonghyo | ko |
dc.contributor.author | Arguelles, Alonso J. | ko |
dc.contributor.author | Khomutnyk, Yaroslav Ya | ko |
dc.contributor.author | Mensah, Enoch | ko |
dc.contributor.author | Guo, Hao | ko |
dc.contributor.author | Hourani, Rami | ko |
dc.contributor.author | Zimmerman, Paul M. | ko |
dc.contributor.author | Nagorny, Pavel | ko |
dc.date.accessioned | 2021-11-30T06:42:21Z | - |
dc.date.available | 2021-11-30T06:42:21Z | - |
dc.date.created | 2021-11-29 | - |
dc.date.created | 2021-11-29 | - |
dc.date.created | 2021-11-29 | - |
dc.date.issued | 2021-11 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.143, no.44, pp.18592 - 18604 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/289675 | - |
dc.description.abstract | This article describes studies on the regioselective acetal protection of monosaccharide-based diols using chiral phosphoric acids (CPAs) and their immobilized polymeric variants, (R)-Ad-TRIP-PS and (S)-SPINOL-PS, as the catalysts. These catalyst-controlled regioselective acetalizations were found to proceed with high regioselectivities (up to >25:1 rr) on various D-glucose-, D-galactose-, D-mannose-, and L-fucose-derived 1,2-diols and could be carried out in a regiodivergent fashion depending on the choice of chiral catalyst. The polymeric catalysts were conveniently recycled and reused multiple times for gram-scale functionalizations with catalytic loadings as low as 0.1 mol %, and their performance was often found to be superior to the performance of their monomeric variants. These regioselective CPA-catalyzed acetalizations were successfully combined with common hydroxyl group functionalizations as single-pot telescoped procedures to produce 32 regioisomerically pure differentially protected mono- and disaccharide derivatives. To further demonstrate the utility of the polymeric catalysts, the same batch of (R)-Ad-TRIP-PS catalyst was recycled and reused to accomplish single-pot gram-scale syntheses of 6 differentially protected D-glucose derivatives. The subsequent exploration of the reaction mechanism using NMR studies of deuterated and nondeuterated substrates revealed that low-temperature acetalizations happen via a syn-addition mechanism and that the reaction regioselectivity exhibits strong dependence on the temperature. The computational studies indicate a complex temperature-dependent interplay of two reaction mechanisms, one involving an anomeric phosphate intermediate and another via concerted asynchronous formation of an acetal, that results in syn-addition products. The computational models also explain the steric factors responsible for the observed C2 selectivities and are consistent with experimentally observed selectivity trends. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Studies of Catalyst-Controlled Regioselective Acetalization and Its Application to Single-Pot Synthesis of Differentially Protected Saccharides | - |
dc.type | Article | - |
dc.identifier.wosid | 000718279300026 | - |
dc.identifier.scopusid | 2-s2.0-85118807283 | - |
dc.type.rims | ART | - |
dc.citation.volume | 143 | - |
dc.citation.issue | 44 | - |
dc.citation.beginningpage | 18592 | - |
dc.citation.endingpage | 18604 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/jacs.1c08448 | - |
dc.embargo.liftdate | 9999-12-31 | - |
dc.embargo.terms | 9999-12-31 | - |
dc.contributor.localauthor | Lee, Jeonghyo | - |
dc.contributor.nonIdAuthor | Wang, Sibin | - |
dc.contributor.nonIdAuthor | Zhelavskyi, Oleksii | - |
dc.contributor.nonIdAuthor | Arguelles, Alonso J. | - |
dc.contributor.nonIdAuthor | Khomutnyk, Yaroslav Ya | - |
dc.contributor.nonIdAuthor | Mensah, Enoch | - |
dc.contributor.nonIdAuthor | Guo, Hao | - |
dc.contributor.nonIdAuthor | Hourani, Rami | - |
dc.contributor.nonIdAuthor | Zimmerman, Paul M. | - |
dc.contributor.nonIdAuthor | Nagorny, Pavel | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | SITE-SELECTIVE ACYLATION | - |
dc.subject.keywordPlus | ASYMMETRIC PHOSPHORYLATION | - |
dc.subject.keywordPlus | OLIGOSACCHARIDE SYNTHESIS | - |
dc.subject.keywordPlus | ACID | - |
dc.subject.keywordPlus | GLYCOSYLATION | - |
dc.subject.keywordPlus | DESYMMETRIZATION | - |
dc.subject.keywordPlus | SILYLATION | - |
dc.subject.keywordPlus | RESOLUTION | - |
dc.subject.keywordPlus | MECHANISM | - |
dc.subject.keywordPlus | ORIGINS | - |
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