Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release
We herein present a strain-release glycosylation method employing a rationally designed ortho-2,2-dimethoxycarbonylcyclopropylbenzyl (CCPB) thioglycoside donor. The donor is activated through the nucleophilic ring-opening of a remotely activable donor-acceptor cyclopropane (DAC) catalyzed by mild Sc...
| Main Authors: | , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2024
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| Online Access: | https://hdl.handle.net/10356/174864 |
| _version_ | 1826121666285010944 |
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| author | Ding, Han Lv, Jian Zhang, Xiao-Lin Xu, Yuan Zhang, Yu-Han Liu, Xue-Wei |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Ding, Han Lv, Jian Zhang, Xiao-Lin Xu, Yuan Zhang, Yu-Han Liu, Xue-Wei |
| author_sort | Ding, Han |
| collection | NTU |
| description | We herein present a strain-release glycosylation method employing a rationally designed ortho-2,2-dimethoxycarbonylcyclopropylbenzyl (CCPB) thioglycoside donor. The donor is activated through the nucleophilic ring-opening of a remotely activable donor-acceptor cyclopropane (DAC) catalyzed by mild Sc(OTf)3. Our new glycosylation method efficiently synthesizes O-, N-, and S-glycosides, providing facile chemical access to the challenging S-glycosides. Because the activation conditions of conventional glycosyl donors and our CCPB thioglycoside are orthogonal, our novel donor is amenable to controlled one-pot glycosylation reactions with conventional donors for expeditious access to complex glycans. The strain-release glycosylation is applied to the assembly of a tetrasaccharide of O-polysaccharide of Escherichia coli O-33 in one pot and the synthesis of a 1,1'-S-linked glycoside oral galectin-3 (Gal-3) inhibitor, TD139, to demonstrate the versatility and effectiveness of the novel method for constructing both O- and S-glycosides. |
| first_indexed | 2024-10-01T05:36:16Z |
| format | Journal Article |
| id | ntu-10356/174864 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:36:16Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1748642024-04-19T15:32:32Z Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release Ding, Han Lv, Jian Zhang, Xiao-Lin Xu, Yuan Zhang, Yu-Han Liu, Xue-Wei School of Chemistry, Chemical Engineering and Biotechnology Chemistry Donor-acceptor cyclopropanes Glycosyl donors We herein present a strain-release glycosylation method employing a rationally designed ortho-2,2-dimethoxycarbonylcyclopropylbenzyl (CCPB) thioglycoside donor. The donor is activated through the nucleophilic ring-opening of a remotely activable donor-acceptor cyclopropane (DAC) catalyzed by mild Sc(OTf)3. Our new glycosylation method efficiently synthesizes O-, N-, and S-glycosides, providing facile chemical access to the challenging S-glycosides. Because the activation conditions of conventional glycosyl donors and our CCPB thioglycoside are orthogonal, our novel donor is amenable to controlled one-pot glycosylation reactions with conventional donors for expeditious access to complex glycans. The strain-release glycosylation is applied to the assembly of a tetrasaccharide of O-polysaccharide of Escherichia coli O-33 in one pot and the synthesis of a 1,1'-S-linked glycoside oral galectin-3 (Gal-3) inhibitor, TD139, to demonstrate the versatility and effectiveness of the novel method for constructing both O- and S-glycosides. Agency for Science, Technology and Research (A*STAR) Ministry of Education (MOE) National Research Foundation (NRF) Published version The authors are grateful to the National Research Foundation (NRF-CRP22-2019-0002), Ministry of Education (MOET2EP30120-0007), and A*A*STAR (A20E5c0087) for financial support to this study. 2024-04-15T01:18:11Z 2024-04-15T01:18:11Z 2024 Journal Article Ding, H., Lv, J., Zhang, X., Xu, Y., Zhang, Y. & Liu, X. (2024). Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release. Chemical Science, 15(10), 3711-3720. https://dx.doi.org/10.1039/d3sc06619c 2041-6520 https://hdl.handle.net/10356/174864 10.1039/d3sc06619c 38455029 2-s2.0-85184608834 10 15 3711 3720 en NRF-CRP22-2019-0002 MOET2EP30120-0007 A20E5c0087 Chemical Science © 2024 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. application/pdf |
| spellingShingle | Chemistry Donor-acceptor cyclopropanes Glycosyl donors Ding, Han Lv, Jian Zhang, Xiao-Lin Xu, Yuan Zhang, Yu-Han Liu, Xue-Wei Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release |
| title | Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release |
| title_full | Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release |
| title_fullStr | Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release |
| title_full_unstemmed | Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release |
| title_short | Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release |
| title_sort | efficient o and s glycosylation with ortho 2 2 dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain release |
| topic | Chemistry Donor-acceptor cyclopropanes Glycosyl donors |
| url | https://hdl.handle.net/10356/174864 |
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