Diastereoselective desymmetric 1,2-cis-glycosylation of meso-diols via chirality transfer from a glycosyl donor
| Autor: | Kazunobu Toshima, Ryoki Yoshida, Kazuki Inaba, Koji Sato, Daisuke Takahashi, Masamichi Tanaka, Nobuya Nishi, Rikuto Oyamada |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
inorganic chemicals
Glycosylation Magnetic Resonance Spectroscopy Carbohydrate chemistry Stereochemistry Science Carbohydrates General Physics and Astronomy Synthetic chemistry methodology Chemistry Techniques Synthetic 010402 general chemistry Phosphatidylinositols 01 natural sciences Desymmetrization General Biochemistry Genetics and Molecular Biology Article chemistry.chemical_compound polycyclic compounds Glycosyl donor lcsh:Science Multidisciplinary 010405 organic chemistry Chemistry Chemical glycosylation Regioselectivity Stereoisomerism General Chemistry 0104 chemical sciences Anti-Bacterial Agents carbohydrates (lipids) Drug Design Mannosides Natural product synthesis lipids (amino acids peptides and proteins) lcsh:Q Chirality (chemistry) Boronic acid |
| Zdroj: | Nature Communications, Vol 11, Iss 1, Pp 1-10 (2020) Nature Communications |
| ISSN: | 2041-1723 |
| Popis: | Chemical desymmetrization reactions of meso-diols are highly effective for the precise and efficient synthesis of chiral molecules. However, even though enzyme-catalyzed desymmetric glycosylations are frequently found in nature, there is no method for highly diastereoselective desymmetric chemical glycosylation of meso-diols. Herein, we report a highly diastereoselective desymmetric 1,2-cis-glycosylation of meso-diols found in myo-inositol 1,3,5-orthoesters using a boronic acid catalyst based on predictions of regioselectivity by density functional theory (DFT) calculations. The enantiotopic hydroxyl groups of the meso-diols are clearly differentiated by the stereochemistry at the C2 position of the glycosyl donor with excellent regioselectivities. In addition, the present method is successfully applied to the synthesis of core structures of phosphatidylinositolmannosides (PIMs) and glycosylphosphatidylinositol (GPI) anchors, and common β-mannoside structures of the LLBM-782 series of antibiotics. Enzyme-catalyzed desymmetric glycosylations are often found in nature, however the corresponding chemical methods are lacking. Here, the authors report a highly diastereoselective desymmetric 1,2-cis-glycosylation of meso-diols found in myo-inositol 1,3,5-orthoesters using a boronic acid catalyst. |
| Databáze: | OpenAIRE |
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