Programmable selective acylation of saccharides mediated by carbene and boronic acid
Chemical synthesis or modification of saccharides remains a major challenge largely because site-selective reactions on their many similar hydroxyl groups are difficult. The lack of efficient chemical synthetic tools has therefore become a main obstacle to understanding saccharide-related biological...
| Main Authors: | , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2022
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| Online Access: | https://hdl.handle.net/10356/161330 |
| _version_ | 1811680642341011456 |
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| author | Lv, Wen-Xin Chen, Hang Zhang, Xinglong Ho, Chang Chin Liu, Yingguo Wu, Shuquan Wang, Haiqi Jin, Zhichao Chi, Robbin Yonggui |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Lv, Wen-Xin Chen, Hang Zhang, Xinglong Ho, Chang Chin Liu, Yingguo Wu, Shuquan Wang, Haiqi Jin, Zhichao Chi, Robbin Yonggui |
| author_sort | Lv, Wen-Xin |
| collection | NTU |
| description | Chemical synthesis or modification of saccharides remains a major challenge largely because site-selective reactions on their many similar hydroxyl groups are difficult. The lack of efficient chemical synthetic tools has therefore become a main obstacle to understanding saccharide-related biological processes and developing saccharide-based pharmaceuticals. Here, we disclose a programmable multilayered selectivity-amplification strategy enabled by boronic acids and N-heterocyclic carbene (NHC) catalysts for site-specific acylation of unprotected monoglycosides. The boronic acids provide transient shielding on certain hydroxyl groups (while simultaneously promoting reactions of other hydroxyl units) via dynamic covalent bonds to offer the first sets of selectivity controls. The NHC catalysts provide further layers of control by mediating selective acylation of the unshielded hydroxyl moieties. Multiple activating and deactivating forces can be easily modulated to yield programmable selectivity patterns. Structurally diverse monosaccharides and their analogs can be precisely reacted with different acylating reagents, leading to quick construction of sophisticated saccharide-derived products. |
| first_indexed | 2024-10-01T03:28:18Z |
| format | Journal Article |
| id | ntu-10356/161330 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:28:18Z |
| publishDate | 2022 |
| record_format | dspace |
| spelling | ntu-10356/1613302023-02-28T20:11:35Z Programmable selective acylation of saccharides mediated by carbene and boronic acid Lv, Wen-Xin Chen, Hang Zhang, Xinglong Ho, Chang Chin Liu, Yingguo Wu, Shuquan Wang, Haiqi Jin, Zhichao Chi, Robbin Yonggui School of Physical and Mathematical Sciences Science::Chemistry Saccharides Polyols Chemical synthesis or modification of saccharides remains a major challenge largely because site-selective reactions on their many similar hydroxyl groups are difficult. The lack of efficient chemical synthetic tools has therefore become a main obstacle to understanding saccharide-related biological processes and developing saccharide-based pharmaceuticals. Here, we disclose a programmable multilayered selectivity-amplification strategy enabled by boronic acids and N-heterocyclic carbene (NHC) catalysts for site-specific acylation of unprotected monoglycosides. The boronic acids provide transient shielding on certain hydroxyl groups (while simultaneously promoting reactions of other hydroxyl units) via dynamic covalent bonds to offer the first sets of selectivity controls. The NHC catalysts provide further layers of control by mediating selective acylation of the unshielded hydroxyl moieties. Multiple activating and deactivating forces can be easily modulated to yield programmable selectivity patterns. Structurally diverse monosaccharides and their analogs can be precisely reacted with different acylating reagents, leading to quick construction of sophisticated saccharide-derived products. Agency for Science, Technology and Research (A*STAR) Ministry of Education (MOE) National Research Foundation (NRF) Submitted/Accepted version We acknowledge funding support from the Singapore National Research Foundation under its NRF Investigatorship (NRF-NRFI2016-06) and Competitive Research Program (NRF-CRP22-2019-0002); the Singapore Ministry of Education under its MOE AcRF Tier 1 Award (RG7/20, RG5/19), MOE AcRF Tier 2 Award (MOE2019- T2-2-117), and MOE AcRF Tier 3 Award (MOE2018-T3-1-003); Nanyang Technological University; the National Natural Science Foundation of China (21772029, 21801051, 21807019, 21961006, 22071036, 22061007, and 22101266); the Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules of the Guizhou Province Department of Education (Qianjiaohe KY (2020)004); the 10 Talent Plan (Shicengci) of Guizhou Province ([2016]5649); the Science and Technology Department of Guizhou Province ([2018]2802 and [2019]1020); the Guizhou University Program of Introducing Talents of Discipline to Universities of China (111 Program, D20023); and Guizhou University. X.Z. acknowledges support from the Agency for Science, Technology and Research(A*STAR) Institute of High Performance Computing and thanks the A*STAR Deputy Chief Executive Research Office for a Career Development Fund (project number C210812008). X.Z. acknowledges the partial use of supercomputers in the A*STAR Computational Resource Center for computations performed in this work. 2022-08-30T08:29:16Z 2022-08-30T08:29:16Z 2022 Journal Article Lv, W., Chen, H., Zhang, X., Ho, C. C., Liu, Y., Wu, S., Wang, H., Jin, Z. & Chi, R. Y. (2022). Programmable selective acylation of saccharides mediated by carbene and boronic acid. Chem, 8(5), 1518-1534. https://dx.doi.org/10.1016/j.chempr.2022.04.019 2451-9308 https://hdl.handle.net/10356/161330 10.1016/j.chempr.2022.04.019 2-s2.0-85130143598 5 8 1518 1534 en NRF-NRFI2016-06 NRF-CRP22-2019-0002 RG7/20 RG5/19 MOE2019- T2-2-117 MOE2018-T3-1-003 Chem © 2022 Elsevier Inc. All rights reserved. This paper was published in Chem and is made available with permission of Elsevier Inc. application/pdf |
| spellingShingle | Science::Chemistry Saccharides Polyols Lv, Wen-Xin Chen, Hang Zhang, Xinglong Ho, Chang Chin Liu, Yingguo Wu, Shuquan Wang, Haiqi Jin, Zhichao Chi, Robbin Yonggui Programmable selective acylation of saccharides mediated by carbene and boronic acid |
| title | Programmable selective acylation of saccharides mediated by carbene and boronic acid |
| title_full | Programmable selective acylation of saccharides mediated by carbene and boronic acid |
| title_fullStr | Programmable selective acylation of saccharides mediated by carbene and boronic acid |
| title_full_unstemmed | Programmable selective acylation of saccharides mediated by carbene and boronic acid |
| title_short | Programmable selective acylation of saccharides mediated by carbene and boronic acid |
| title_sort | programmable selective acylation of saccharides mediated by carbene and boronic acid |
| topic | Science::Chemistry Saccharides Polyols |
| url | https://hdl.handle.net/10356/161330 |
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