Can Side-Chain Conformation and Glycosylation Selectivity of Hexopyranosyl Donors Be Controlled with a Dummy Ligand?
The use of a phenylthio group (SPh) as a dummy ligand at the 6-position to control the side-chain conformation of a series of hexopyranosyl donors is described. The SPh group limits side-chain conformation in a configuration-specific manner, which parallels that seen in the heptopyranosides, and so influences glycosylation selectivity. With both d- and l-glycero-d-galacto-configured donors, the equatorial products are highly favored as they are with an l-glycero-d-gluco donor. For the d-glycero-d-gluco donor, on the other hand, modest axial selectivity is observed. Selectivity patterns are discussed in terms of the side-chain conformation of the donors in combination with the electron-withdrawing effect of the thioacetal group. After glycosylation, removal of the thiophenyl moiety and hydrogenolytic deprotection is achieved in a single step with Raney nickel.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:88 |
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| Enthalten in: |
The Journal of organic chemistry - 88(2023), 6 vom: 17. März, Seite 3678-3696 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Upadhyaya, Kapil [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 17.03.2023 Date Revised 25.03.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.joc.2c02889 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM353834548 |
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| 245 | 1 | 0 | |a Can Side-Chain Conformation and Glycosylation Selectivity of Hexopyranosyl Donors Be Controlled with a Dummy Ligand? |
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| 500 | |a Date Completed 17.03.2023 | ||
| 500 | |a Date Revised 25.03.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a The use of a phenylthio group (SPh) as a dummy ligand at the 6-position to control the side-chain conformation of a series of hexopyranosyl donors is described. The SPh group limits side-chain conformation in a configuration-specific manner, which parallels that seen in the heptopyranosides, and so influences glycosylation selectivity. With both d- and l-glycero-d-galacto-configured donors, the equatorial products are highly favored as they are with an l-glycero-d-gluco donor. For the d-glycero-d-gluco donor, on the other hand, modest axial selectivity is observed. Selectivity patterns are discussed in terms of the side-chain conformation of the donors in combination with the electron-withdrawing effect of the thioacetal group. After glycosylation, removal of the thiophenyl moiety and hydrogenolytic deprotection is achieved in a single step with Raney nickel | ||
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| 700 | 1 | |a Crich, David |e verfasserin |4 aut | |
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