Sen Sumit, Kundu Suman, Pasari Sandip, Hotha Srinivas
Department of Chemistry, Indian Institute of Science Education and Research Pune, Pune, 411 008, India.
Commun Chem. 2024 Apr 2;7(1):73. doi: 10.1038/s42004-024-01152-z.
Post-synthetic surgical editing enables synthesizing diverse molecules from a common scaffold. Editing carbohydrates by inserting a foreign glycan is still a far-reaching goal for synthetic chemists. In this study, a one-pot-three-step chemical approach was employed to edit glycoconjugates. It is comprised of three steps: the first is a 'cut' step, cleaving one of the interglycosidic bonds and producing an intermediate that could be intercepted with 4-mercaptotoluene; second step activates the thiotolyl glycoside in the presence of an aglycon containing an orthogonally activatable ethynylcycloxyl carbonate moiety; and the third step involves 'stitching' by activating the carbonate donor. The cut-insert stitch-editing reaction (CIStER) is demonstrated by inserting branched and linear arabinans reminiscent of M. tuberculosis cell wall from the same designer trimannoside. Glycosylating an activated hydroxyacid (serinyl, steroidal, and lipid) after cutting the interglycosidic bond and stitching in the presence of base extendes the CIStER approach to the synthesis of glycohybrids.
合成后手术编辑能够从一个共同的支架合成多种分子。通过插入外源聚糖来编辑碳水化合物对于合成化学家来说仍然是一个长远的目标。在本研究中，采用了一种一锅三步化学方法来编辑糖缀合物。它包括三个步骤：第一步是“切割”步骤，切断糖苷键之一并产生一种中间体，该中间体可以与4-巯基甲苯反应；第二步在含有可正交活化的乙炔基环氧基碳酸酯部分的苷元存在下活化硫代甲苯基糖苷；第三步是通过活化碳酸酯供体进行“缝合”。通过从相同的设计三甘露糖苷中插入类似于结核分枝杆菌细胞壁的支链和线性阿拉伯聚糖，证明了切割-插入-缝合编辑反应（CIStER）。在切割糖苷键并在碱存在下进行缝合后，将活化的羟基酸（丝氨酰基、甾体和脂质）糖基化，将CIStER方法扩展到糖杂合物的合成。
