TY - JOUR
T1 - Diastereoselective desymmetric 1,2-cis-glycosylation of meso-diols via chirality transfer from a glycosyl donor
AU - Tanaka, Masamichi
AU - Sato, Koji
AU - Yoshida, Ryoki
AU - Nishi, Nobuya
AU - Oyamada, Rikuto
AU - Inaba, Kazuki
AU - Takahashi, Daisuke
AU - Toshima, Kazunobu
PY - 2020/12/1
Y1 - 2020/12/1
N2 - 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.
AB - 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.
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U2 - 10.1038/s41467-020-16365-8
DO - 10.1038/s41467-020-16365-8
M3 - Article
C2 - 32415161
AN - SCOPUS:85084785613
VL - 11
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 2431
ER -