Diastereoselective desymmetric 1,2-cis-glycosylation of meso-diols via chirality transfer from a glycosyl donor

• Published in: Nature communications 2020-05, Vol.11 (1), p.2431-2431, Article 2431
• Main Authors: Tanaka, Masamichi, Sato, Koji, Yoshida, Ryoki, Nishi, Nobuya, Oyamada, Rikuto, Inaba, Kazuki, Takahashi, Daisuke, Toshima, Kazunobu
• Format: Article
• Language: English
• Subjects: 119/118; 140/131; 140/58; 639/638/403/931; 639/638/403/977; 639/638/549/933; Anti-Bacterial Agents - chemical synthesis; Anti-Bacterial Agents - chemistry; Antibiotics; Carbohydrates - chemistry; Catalysts; Chemical reactions; Chemical synthesis; Chemistry Techniques, Synthetic; Chirality; Density functional theory; Diols; Drug Design; Enzymes; Glycosylation; Glycosylphosphatidylinositol; Humanities and Social Sciences; Hydroxyl groups; Inositol; Magnetic Resonance Spectroscopy; Mannosides - chemistry; multidisciplinary; Orthoesters; Phosphatidylinositols - chemistry; Regioselectivity; Science; Science (multidisciplinary); Stereochemistry; Stereoisomerism; Stereoselectivity
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-16365-8

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.