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Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy

While strategies involving a 2e(−) transfer pathway have dictated glycosylation development, the direct glycosylation of readily accessible glycosyl donors as radical precursors is particularly appealing because of high radical anomeric selectivity and atom- and step-economy. However, the developmen...

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Detalles Bibliográficos
Autores principales: Ji, Peng, Zhang, Yueteng, Gao, Feng, Bi, Fangchao, Wang, Wei
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8163235/
https://www.ncbi.nlm.nih.gov/pubmed/34094490
http://dx.doi.org/10.1039/d0sc04136j
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author Ji, Peng
Zhang, Yueteng
Gao, Feng
Bi, Fangchao
Wang, Wei
author_facet Ji, Peng
Zhang, Yueteng
Gao, Feng
Bi, Fangchao
Wang, Wei
author_sort Ji, Peng
collection PubMed
description While strategies involving a 2e(−) transfer pathway have dictated glycosylation development, the direct glycosylation of readily accessible glycosyl donors as radical precursors is particularly appealing because of high radical anomeric selectivity and atom- and step-economy. However, the development of the radical process has been challenging owing to notorious competing reduction, elimination and/or S(N) side reactions of commonly used, labile glycosyl donors. Here we introduce an organophotocatalytic strategy through which glycosyl bromides can be efficiently converted into corresponding anomeric radicals by photoredox mediated HAT catalysis without a transition metal or a directing group and achieve highly anomeric selectivity. The power of this platform has been demonstrated by the mild reaction conditions enabling the synthesis of challenging α-1,2-cis-thioglycosides, the tolerance of various functional groups and the broad substrate scope for both common pentoses and hexoses. Furthermore, this general approach is compatible with both sp(2) and sp(3) sulfur electrophiles and late-stage glycodiversification for a total of 50 substrates probed.
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spelling pubmed-81632352021-06-04 Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy Ji, Peng Zhang, Yueteng Gao, Feng Bi, Fangchao Wang, Wei Chem Sci Chemistry While strategies involving a 2e(−) transfer pathway have dictated glycosylation development, the direct glycosylation of readily accessible glycosyl donors as radical precursors is particularly appealing because of high radical anomeric selectivity and atom- and step-economy. However, the development of the radical process has been challenging owing to notorious competing reduction, elimination and/or S(N) side reactions of commonly used, labile glycosyl donors. Here we introduce an organophotocatalytic strategy through which glycosyl bromides can be efficiently converted into corresponding anomeric radicals by photoredox mediated HAT catalysis without a transition metal or a directing group and achieve highly anomeric selectivity. The power of this platform has been demonstrated by the mild reaction conditions enabling the synthesis of challenging α-1,2-cis-thioglycosides, the tolerance of various functional groups and the broad substrate scope for both common pentoses and hexoses. Furthermore, this general approach is compatible with both sp(2) and sp(3) sulfur electrophiles and late-stage glycodiversification for a total of 50 substrates probed. The Royal Society of Chemistry 2020-10-19 /pmc/articles/PMC8163235/ /pubmed/34094490 http://dx.doi.org/10.1039/d0sc04136j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Ji, Peng
Zhang, Yueteng
Gao, Feng
Bi, Fangchao
Wang, Wei
Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
title Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
title_full Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
title_fullStr Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
title_full_unstemmed Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
title_short Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
title_sort direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8163235/
https://www.ncbi.nlm.nih.gov/pubmed/34094490
http://dx.doi.org/10.1039/d0sc04136j
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