Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight
Herein, we devised a method for stereoselective O-glycosylation using an Ir(I)-catalyst which enables both hydroalkoxylation and nucleophilic substitution of glycals with varying substituents at the C3 position. In this transformation, 2-deoxy-α-O-glycosides were acquired when glycals equipped with...
| Main Authors: | , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2021
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| Online Access: | https://hdl.handle.net/10356/147077 |
| _version_ | 1811697103669297152 |
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| author | Pal, Kumar Bhaskar Guo, Aoxin Das, Mrinmoy Lee, Jiande Báti, Gábor Yip, Benjamin Rui Peng Loh, Teck-Peng Liu, Xue-Wei |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Pal, Kumar Bhaskar Guo, Aoxin Das, Mrinmoy Lee, Jiande Báti, Gábor Yip, Benjamin Rui Peng Loh, Teck-Peng Liu, Xue-Wei |
| author_sort | Pal, Kumar Bhaskar |
| collection | NTU |
| description | Herein, we devised a method for stereoselective O-glycosylation using an Ir(I)-catalyst which enables both hydroalkoxylation and nucleophilic substitution of glycals with varying substituents at the C3 position. In this transformation, 2-deoxy-α-O-glycosides were acquired when glycals equipped with a notoriously poor leaving group at C3 were used; in contrast 2,3-unsaturated-α-O-glycosides were produced from glycals that bear a good leaving group at C3. Mechanistic studies indicate that both reactions proceed via the directing mechanism, through which the acceptor coordinates to the Ir(I) metal in the α-face-coordinated Ir(I)-glycal π-complex and then attacks the glycal that contains the O-glycosidic bond in a syn-addition manner. This protocol exhibits good functional group tolerance and is exemplified with the preparation of a library of oligosaccharides in moderate to high yields and with excellent stereoselectivities. |
| first_indexed | 2024-10-01T07:49:56Z |
| format | Journal Article |
| id | ntu-10356/147077 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:49:56Z |
| publishDate | 2021 |
| record_format | dspace |
| spelling | ntu-10356/1470772023-02-28T19:53:21Z Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight Pal, Kumar Bhaskar Guo, Aoxin Das, Mrinmoy Lee, Jiande Báti, Gábor Yip, Benjamin Rui Peng Loh, Teck-Peng Liu, Xue-Wei School of Physical and Mathematical Sciences Nanyang Environment and Water Research Institute Science::Chemistry Stereoselective O-glycosylation Ir(I)-catalyst Herein, we devised a method for stereoselective O-glycosylation using an Ir(I)-catalyst which enables both hydroalkoxylation and nucleophilic substitution of glycals with varying substituents at the C3 position. In this transformation, 2-deoxy-α-O-glycosides were acquired when glycals equipped with a notoriously poor leaving group at C3 were used; in contrast 2,3-unsaturated-α-O-glycosides were produced from glycals that bear a good leaving group at C3. Mechanistic studies indicate that both reactions proceed via the directing mechanism, through which the acceptor coordinates to the Ir(I) metal in the α-face-coordinated Ir(I)-glycal π-complex and then attacks the glycal that contains the O-glycosidic bond in a syn-addition manner. This protocol exhibits good functional group tolerance and is exemplified with the preparation of a library of oligosaccharides in moderate to high yields and with excellent stereoselectivities. National Research Foundation (NRF) Published version We thank the Nanyang Technological University (RG9/20) and National Research Foundation (NRF2016NRF-NSFC002-005), Singapore for their financial support. 2021-03-23T02:11:45Z 2021-03-23T02:11:45Z 2021 Journal Article Pal, K. B., Guo, A., Das, M., Lee, J., Báti, G., Yip, B. R. P., Loh, T. & Liu, X. (2021). Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight. Chemical Science, 12(6), 2209-2216. https://dx.doi.org/10.1039/D0SC06529C 2041-6520 https://hdl.handle.net/10356/147077 10.1039/D0SC06529C 6 12 2209 2216 en NRF2016NRF-NSFC002-005 Chemical Science © 2021 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 | Science::Chemistry Stereoselective O-glycosylation Ir(I)-catalyst Pal, Kumar Bhaskar Guo, Aoxin Das, Mrinmoy Lee, Jiande Báti, Gábor Yip, Benjamin Rui Peng Loh, Teck-Peng Liu, Xue-Wei Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight |
| title | Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight |
| title_full | Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight |
| title_fullStr | Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight |
| title_full_unstemmed | Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight |
| title_short | Iridium-promoted deoxyglycoside synthesis : stereoselectivity and mechanistic insight |
| title_sort | iridium promoted deoxyglycoside synthesis stereoselectivity and mechanistic insight |
| topic | Science::Chemistry Stereoselective O-glycosylation Ir(I)-catalyst |
| url | https://hdl.handle.net/10356/147077 |
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