Studies of Catalyst-Controlled Regioselective Acetalization and Its Application to Single-Pot Synthesis of Differentially Protected Saccharides
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Wang, Sibin | - |
dc.contributor.author | Zhelavskyi, Oleksii | - |
dc.contributor.author | Lee, Jeonghyo | - |
dc.contributor.author | Arguelles, Alonso J. | - |
dc.contributor.author | Khomutnyk, Yaroslav Ya | - |
dc.contributor.author | Mensah, Enoch | - |
dc.contributor.author | Guo, Hao | - |
dc.contributor.author | Hourani, Rami | - |
dc.contributor.author | Zimmerman, Paul M | - |
dc.contributor.author | Nagorny, Pavel | - |
dc.date.accessioned | 2023-08-16T08:08:43Z | - |
dc.date.available | 2023-08-16T08:08:43Z | - |
dc.date.created | 2023-07-21 | - |
dc.date.issued | 2021-11 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | https://scholarworks.bwise.kr/hanyang/handle/2021.sw.hanyang/189282 | - |
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 | 영어 | - |
dc.language.iso | en | - |
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.contributor.affiliatedAuthor | Lee, Jeonghyo | - |
dc.identifier.doi | 10.1021/jacs.1c08448 | - |
dc.identifier.scopusid | 2-s2.0-85118807283 | - |
dc.identifier.wosid | 000718279300026 | - |
dc.identifier.bibliographicCitation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.143, no.44, pp.18592 - 18604 | - |
dc.relation.isPartOf | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.citation.title | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.citation.volume | 143 | - |
dc.citation.number | 44 | - |
dc.citation.startPage | 18592 | - |
dc.citation.endPage | 18604 | - |
dc.type.rims | ART | - |
dc.type.docType | 정기학술지(Article(Perspective Article포함)) | - |
dc.description.journalClass | 1 | - |
dc.description.isOpenAccess | Y | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalWebOfScienceCategory | Categories Chemistry, Multidisciplinary | - |
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 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/jacs.1c08448 | - |
Items in ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.
222, Wangsimni-ro, Seongdong-gu, Seoul, 04763, Korea+82-2-2220-1365
COPYRIGHT © 2021 HANYANG UNIVERSITY.
Certain data included herein are derived from the © Web of Science of Clarivate Analytics. All rights reserved.
You may not copy or re-distribute this material in whole or in part without the prior written consent of Clarivate Analytics.