O-(2-O-acetyl-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-mannopyranosyl) trichloroacetimidate | 220734-62-3

• 英文名称: O-(2-O-acetyl-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-mannopyranosyl) trichloroacetimidate
• 英文别名: 2-O-acetyl-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-mannopyranosyl trichloroacetimidate；Bn(-3)[Bn(-4)][TBDPS(-6)]Man2Ac(a)-O-C(NH)CCl3；[(2R,3S,4S,5R,6R)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-4,5-bis(phenylmethoxy)-2-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] acetate
• CAS: 220734-62-3
• 化学式: C₄₀H₄₄Cl₃NO₇Si
• 分子量: 785.236
• InChiKey: CJIIRFDSPPZISN-GDWCTEMXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.75
• 重原子数：
  52
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  96.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  O-(2-O-acetyl-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-mannopyranosyl) trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 、 3 A molecular sieve 、 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.25h， 生成 allyl 2-O-allyl-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside
  参考文献：
  名称：

  基于多功能构建块的糖基磷脂酰肌醇 (GPI) 锚定合成——酵母 GPI 锚定的全合成

  摘要：

  对于目标分子 1 的合成设计，逆合成分析产生了结构单元 2-5，其中已知神经酰胺 2-亚磷酸酯衍生物 2 和氨基乙基亚磷酸酯衍生物 5。α-葡糖胺基 (16) 肌醇结构单元 3 的生成基于假二糖 6，其在 6b-O 处选择性苯甲酰化，然后在 3b-O 处选择性苄基化得到 3。四甘露糖基结构单元 4 的合成从已知的原酸酯开始衍生物 8 被转化为多功能甘露糖供体 13 和 18 以及受体 22。13 与 22 反应得到 α-二糖 23，脱乙酰然后与 18 甘露糖基化得到三糖 25；随后用 13 脱乙酰和甘露糖基化得到四糖 27；去酰化、乙酰化、区域选择性去除异头 O-乙酰基并用 CCl3CN/DBU 处理得到 4。3 与供体 4 的糖基化以高产率得到假六糖 31。用 O-苄基取代 O-酰基，然后用 O-乙酰基交换薄荷氧羰基得到 36，这使得 2 和 5 能够区域选择性连接。为此，去除 6e-O

  DOI：

  10.1002/(sici)1099-0690(199905)1999:5<1153::aid-ejoc1153>3.0.co;2-s
• 作为产物：
  描述：

  3,4-Di-O-benzyl-6-O-tert-butyldiphenylsilyl-1,2-O-(methyl-orthoacetyl)-β-D-mannopyranose 在 吡啶 、 碳酸氢铵 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 生成 O-(2-O-acetyl-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-mannopyranosyl) trichloroacetimidate
  参考文献：
  名称：

  Mayer, Thomas G.; Kratzer, Bernd; Schmidt, Richard R., Angewandte Chemie, 1994, vol. 106, # 21, p. 2289 - 2293

  摘要：

  DOI：

文献信息

• A Variable Concept for the Preparation of Branched Glycosyl Phosphatidyl Inositol Anchors
  作者：Klaus Pekari、Richard R. Schmidt

  DOI：10.1021/jo026380j

  日期：2003.2.1

  A variable concept for the synthesis of branched glycosyl phosphatidyl inositol (GPI) anchors was established. Its efficiency could be shown by the successful synthesis of the GPI anchor of rat brain Thy-1 and of the scrapie prion protein both in the water soluble 1c and lipidated form 1a. Retrosynthesis led to building blocks 2-6 of which 5 could be further disconnected to building blocks 7-9. Trichloroacetimidate

  建立了用于合成支链糖基磷脂酰肌醇（GPI）锚的可变概念。它的效率可以通过成功合成大鼠脑Thy-1的GPI锚和水溶性1c和脂化形式1a的刮the病毒蛋白来证明。逆向合成导致结构单元2-6，其中5可以进一步断开与结构单元7-9的连接。使用已知的糖基供体7和8从糖基受体9开始以直接的方式构建三氯乙酰亚胺酸5。然后通过将伪二糖受体6与供体5进行糖基化组装碳水化合物骨架。为确保糖基化反应中的高立体选择性和高收率，使用了辅助的辅助疗法。连续脱保护并引入各种磷酸盐残基，得到了完全保护的GPI锚。Boc保护基的催化氢化和酸催化裂解提供了目标分子，可以在结构上进行完全分配。
• Synthesis of the Fully Phosphorylated GPI Anchor Pseudohexasaccharide of <i>Toxoplasma </i><i>g</i><i>ondii</i>
  作者：Klaus Pekari、Denis Tailler、Ralf Weingart、Richard R. Schmidt

  DOI：10.1021/jo015840q

  日期：2001.11.1

  stereoselectivity and good yields in the glycosylation reactions, anchimeric assistance was employed. To enable regioselective attachment of the two different phosphorus esters, the 6f-O-silyl group of 32 was first removed and the aminoethyl phosphate residue was attached. Then the MPM group was oxidatively removed, and the second phosphate residue was introduced. Unprotected 1a was then liberated in two steps:

  完全磷酸化的糖基磷脂酰肌醇（GPI）锚定假六糖1a的逆合成导致了结构单元2-6，其中5和6是已知的。假二糖结构单元2的形成基于容易获得的结构单元7，该结构单元7通过衍生物11及其与已知供体12的糖基化作用，获得了所需的化合物2。结构单元3，允许所需的所有羟基进入，由甘露糖分五个步骤制备。从容易获得的前体中获得结构单元4，该结构单元4与3反应生成二糖23。决定性假六糖中间体32的合成基于23与5，然后与6，最后与2的反应。由于在糖基化反应中具有高的立体选择性和良好的收率，因此使用了嵌合助剂。为了使两种不同的磷酸酯区域选择性地连接，首先除去32的6f-O-甲硅烷基，并连接磷酸氨基乙基残基。然后，氧化除去MPM基团，并引入第二磷酸盐残基。然后分两步释放未保护的1a：用甲醇钠处理除去了乙酰基保护基团，最后，催化氢化得到了所需的目标分子，该分子可以在结构上完全分配。
• Phosphatidylinositol mannosides: Synthesis and adjuvant properties of phosphatidylinositol di- and tetramannosides
  作者：Gary D. Ainge、Natalie A. Parlane、Michel Denis、Colin M. Hayman、David S. Larsen、Gavin F. Painter

  DOI：10.1016/j.bmc.2006.07.003

  日期：2006.11

  Phosphatidylinositol mannosides (PIMs) isolated from mycobacteria have been identified as an important class of glycolipids with significant immune modulating properties. We present here the syntheses of phosphatidylinositol dimannoside (PIM2, 1) and phosphatidylinositol tetramannoside (PIM4, 2) and evaluate their adjuvant properties in a transgenic mouse model. The key step in the synthetic methodology

  从分枝杆菌中分离出的磷脂酰肌醇甘露糖苷（PIM）已被确定为一类重要的糖脂，具有重要的免疫调节特性。我们在这里介绍磷脂酰肌醇二甘露糖苷（PIM2，1）和磷脂酰肌醇四甘露糖苷（PIM4，2）的合成，并在转基因小鼠模型中评估其佐剂特性。合成2的合成方法学中的关键步骤取决于二醇3与甘露糖基供体11的选择性糖基化。当与模型抗原一起作为佐剂使用时，两种合成的PIM均可有效增强IFN-γ，PIM2更具活性。这些数据表明，在该测定中，PIM核心结构负责观察到的生物活性。
• Synthesis of the glycosyl phosphatidyl inositol anchor of rat brain Thy-1
  作者：Denis Tailler、Vincent Ferrières、Klaus Pekari、Richard R. Schmidt

  DOI：10.1016/s0040-4039(98)02579-9

  日期：1999.1

  Disintegration of the target molecule 1 into building blocks A-E was performed. For D, an efficient synthesis of mannose derivative 5, representing mannose residue c in the target molecule, could be performed; 5 permits the required regioselective access to C-1, 2-O, 4-O, and 6-O. Reaction of 5 with galactosamine donor 3 led to D in high yield. E could be readily prepared from known mannosyl donors

  进行目标分子1的分解成结构单元AE。对于D，可以进行代表目标分子中甘露糖残基c的甘露糖衍生物5的有效合成。5允许对C -1、2- O，4- O和6- O进行区域选择性访问。的反应5与半乳糖胺供体3导致d以高收率。E可以很容易地从已知的甘露糖基供体7和9制备。AE组合仅在十一个高产率的步骤中导致了完全被O-苄基保护的靶分子14，因此展现了这种会聚策略的效率，该策略提供了靶分子1。
• Synthetic Analogues of Glycosylphosphatidylinositol-Anchored Proteins and Their Behavior in Supported Lipid Bilayers
  作者：Margot G. Paulick、Amber R. Wise、Martin B. Forstner、Jay T. Groves、Carolyn R. Bertozzi

  DOI：10.1021/ja073271j

  日期：2007.9.1

  Positioned at the C-terminus of many eukaryotic proteins, the glycosylphosphaticlylinositol (GPI) anchor is a posttranslational modification that anchors the modified proteins in the outer leaflet of the plasma membrane. GPI-anchored proteins play vital roles in signal transcluction, the vertebrate immune response, and the pathobiology of trypanosomal parasites. While many GPI-anchored proteins have been characterized, the biological functions of the GPI anchor have yet to be elucidated at a molecular level. We synthesized a series of GPI-protein analogues bearing modified anchor structures that were designed to dissect the contribution of various glycan components to the GPI-protein's membrane behavior. These anchor analogues were similar in length to native GPI anchors and included mimics of the native structure's three domains. A combination of expressed protein ligation and native chemical ligation was used to attach these analogues to the green fluorescent protein (GFP). These modified GFPs were incorporated in supported lipid bilayers, and their mobilities were analyzed using fluorescence correlation spectroscopy. The data from these experiments suggest that the GPI anchor is more than a simple membrane-anchoring device; it also may prevent transient interactions between the attached protein and the underlying lipid bilayer, thereby permitting rapid diffusion in the bilayer. The ability to generate chemically defined analogues of GPI-anchored proteins is an important step toward elucidating the molecular functions of this interesting post-translational modification.