Diastereoselective desymmetric 1,2-cis-glycosylation of meso-diols via chirality transfer from a glycosyl donor
Diastereoselective desymmetric 1,2-cis-glycosylation of meso-diols via chirality transfer from a glycosyl donor
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通过糖基供体的手性转移对内消旋二醇进行非对映选择性不对称 1,2-顺式糖基化
DOI：
10.1038/s41467-020-16365-8
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发表时间：
2020
影响因子：
16.6
通讯作者：
Toshima Kazunobu
中科院分区：
文献类型：
--
作者：
Tanaka Masamichi;Sato Koji;Yoshida Ryoki;Nishi Nobuya;Oyamada Rikuto;Inaba Kazuki;Takahashi Daisuke;Toshima Kazunobu
内消旋二醇的化学去对称化反应是精确、高效合成手性分子的有效方法。然而，尽管酶催化的去对称糖基化反应在自然界中经常被发现，但还没有用于内消旋二醇的高度非对映选择性去对称化学糖基化的方法。在此，我们报告了一个高度非对映选择性dessymmetric 1，2-cis-glycosylation meso-diols发现inmyo-inositol 1，3，5-orthoesters使用硼酸催化剂的基础上预测的区域选择性密度泛函理论（DFT）计算。通过糖基给体C2位的立体化学，可以清楚地区分两种间二醇的对映体羟基，并具有良好的区域选择性。此外，本方法成功地应用于磷脂酰肌醇甘露糖苷（PIM）和糖基磷脂酰肌醇（GPI）锚的核心结构的合成，以及LLBM-782系列抗生素的常见β-甘露糖苷结构的合成。
Chemical desymmetrization reactions ofmeso-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 ofmeso-diols. Herein, we report a highly diastereoselective desymmetric 1,2-cis-glycosylation ofmeso-diols found inmyo-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 themeso-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.