ethyl 2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside | 289057-12-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
• 英文别名: (2R,3S,4S,5S,6R)-2-ethylsulfanyl-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-ol
• CAS: 289057-12-1
• 化学式: C₂₉H₃₄O₅S
• 分子量: 494.652
• InChiKey: BLEKONIUPDUQSX-FYYQJAJYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside 在 4-二甲氨基吡啶 、 DMTST 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 0.92h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(2,4,6-tri-O-benzyl-3-O-picoloyl-α/β-D-mannopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Hydrogen-Bond-Mediated Aglycone Delivery: Focus on β-Mannosylation

  摘要：

  O-Picoloyl groups at remote positions can mediate the course of glycosylation reactions by providing high facial selectivity for the H-bond-mediated attack of the glycosyl acceptor. A new practical method for the stereoselective synthesis of beta-mannosides at ambient temperature is presented.

  DOI：

  10.1021/ol403396j
• 作为产物：
  描述：

  ethyl 2,3-di-O-isopropylidene-1-thio-α-D-mannopyranoside 在 sodium hydroxide 、 四丁基硫酸氢铵 、 sodium hydride 、 溶剂黄146 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.5h， 生成 ethyl 2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  摘要：

  A series of prearranged glycosides 5, 17, 23, 28, 37 and 41, having a benzyl-protected 1-thiomannosyl donor linked through its positions 2, 3, 4 and 6 via succinate and malonate tethers, respectively, to positions 2, 3, and 6 of a benzyl glucopyranoside acceptor, were prepared by condensation of the respective mannosyl succinates and malonates with suitably protected benzyl glucopyranosides. The prearranged glycosides were intramolecularly coupled under various conditions to give the corresponding, tethered (1 --> 4)-linked disaccharides The yields and anomer ratios of the products of these couplings were interpreted in terms of the thermodynamic stability of the resulting disaccharides. In the case of prearranged glycoside 17, having positions 3 of both the donor and the acceptor linked by a succinate tether, a strong dependence of the diastereoselectivity of the intramolecular glycosylation on the activation procedure was observed. All other cases did not show a significant dependence of the outcome of the anomeric configuration in intramolecular glycosylation on the activation procedure or the solvent.

  DOI：

  10.1002/1522-2675(20001004)83:10<2655::aid-hlca2655>3.0.co;2-u

文献信息

• Chemical Synthesis Elucidates the Key Antigenic Epitope of the Autism‐Related Bacterium <i>Clostridium bolteae</i> Capsular Octadecasaccharide
  作者：Juntao Cai、Jing Hu、Chunjun Qin、Lingxin Li、Dacheng Shen、Guangzong Tian、Xiaopeng Zou、Peter H. Seeberger、Jian Yin

  DOI：10.1002/anie.202007209

  日期：2020.11.9

  spectrum disorder (ASD). To create vaccines against C. bolteae, it is important to identify exact protective epitopes of the immunologically active capsular polysaccharide (CPS). Here, a series of C. bolteae CPS glycans, up to an octadecasaccharide, was prepared. Key to achieving the total syntheses is a [2+2] coupling strategy based on a β‐d‐Rhap‐(1→3)‐α‐d‐Manp repeating unit that in turn was accessed by

  肠道病原体梭状芽胞杆菌与自闭症谱系障碍（ASD）的发作有关。要创建针对螺栓念珠菌的疫苗，重要的是要确定具有免疫活性的荚膜多糖（CPS）的确切保护表位。在这里，制备了一系列的紫花C. CPS聚糖，直至十八糖。键实现的全合成是[2 + 2]根据一个β-偶联策略d -RHA p - （1→3）-α- d -Man p重复单元，其又被立体选择性β-访问d鼠李糖基化。4,6‐ O亚苄基诱导的构象锁定是形成β- d-甘露糖型糖苷的强大策略。通过Swern氧化和硼氢化物还原有效地实现了基于C2差向异构化的β- d-奎奴诺酮的间接策略。顺序糖基化，区域选择性和整体脱保护产生了二糖和四糖，直至十八糖。对灭活的克雷伯氏菌进行免疫的兔血清的糖微阵列分析显示对二糖和四糖有体液免疫反应，但没有更长的序列。四糖可能是设计抗克氏梭菌的糖结合疫苗的关键主题。
• Synthesis of an Inositol Phosphoglycan Fragment found in Leishmania Parasites
  作者：Katinka Ruda、Jan Lindberg、Per J Garegg、Stefan Oscarson、Peter Konradsson

  DOI：10.1016/s0040-4020(00)00239-8

  日期：2000.6

  with 2,3,4,6-tetra-O-benzyl-α-d-glucopyranos-1-yl H-phosphonate to form the protected target molecule 12. Deprotection of 12 by acidic deacetalisation/desilylation and subsequent catalytic hydrogenolysis resulted in cleavage of the anomeric phosphodiester to produce 1. Debenzylation with sodium in liquid ammonia followed by acidic deacetalisation/desilylation gave the target compound 2a.

  的合成1和图2a是使用块合成策略描述。化合物4被用作两个甘露糖衍生物的前体，这两个甘露糖衍生物耦合在一起，形成了双甘露糖苷结构单元。硫代糖苷7与8偶联生成肌醇磷酸聚糖9a，将其选择性脱保护并与2,3,4,6-四-O-苄基-α-d-吡喃葡萄糖-1-基H-膦酸酯反应形成受保护的靶分子12。通过酸性脱缩醛/去甲硅烷基化作用对12进行脱保护并随后进行催化氢解反应，导致端基异构磷酸二酯裂解生成1。在液体氨中用钠脱苄基，然后进行酸性脱缩醛/去甲硅烷基化，得到目标化合物2a。