methyl 2,4-di-O-benzyl-3,6-di-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl)-α-D-mannopyranoside | 493008-73-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,4-di-O-benzyl-3,6-di-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl)-α-D-mannopyranoside
• 英文别名: Bz(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Man(a1-3)[Bz(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Man(a1-6)][Bn(-2)][Bn(-4)]a-Man1Me；[(2S,3S,4S,5R,6R)-2-[[(2R,3R,4S,5S,6S)-4-[(2R,3S,4S,5R,6R)-3-benzoyloxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxy-6-methoxy-3,5-bis(phenylmethoxy)oxan-2-yl]methoxy]-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] benzoate
• CAS: 493008-73-4
• 化学式: C₈₉H₉₀O₁₈
• 分子量: 1447.68
• InChiKey: YNADXVIIIRHZMR-DNKMNQPBSA-N

物化性质

• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.8
• 重原子数：
  107
• 可旋转键数：
  38
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  182
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  methyl 2,4-di-O-benzyl-3,6-di-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl)-α-D-mannopyranoside 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.0h， 以95%的产率得到methyl 2,4-di-O-benzyl-3,6-di-O-(3,4,6-tri-O-benzyl-α-D-mannopyranosyl)-α-D-mannopyranoside
  参考文献：
  名称：

  通过远程活化羟基苯并三唑基糖苷产生核苷的糖苷化反应

  摘要：

  羟基苯并三唑因其增加的反应性而通常用于肽化学中，以减少外消旋作用。在本文中，鉴定出非常稳定的羟基苯并三唑基葡糖苷可以进行糖苷化。假设该反应通过Tf 2进行远程激活在HOBt的N3位点为O，接着是被糖基受体攻击的氧碳鎓离子的挤出。此外，两性离子苯并三唑基物质的平衡使离去基团失去竞争性，并产生已被重新转化为糖基供体的核沉子。该反应温和，高产率，快速并且适合于同时含有C2-醚和C2-酯的供体。再生供体糖苷化策略是有前途的，因为它使我们能够再生糖基供体以供进一步利用。通过成功合成HIV1-gp120复合物的支链五聚甘露聚糖核心，证明了该方法在寡糖合成中的实用性。

  DOI：

  10.1021/acs.joc.7b02027
• 作为产物：
  描述：

  甲基2,4-二-O-苄基吡喃己糖苷 、 ethyl 2-O-benzoyl-3,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside 在 4 A molecular sieve 、 tris(p-bromophenylammoniumyl) hexachloroantimonate 作用下， 生成 methyl 2,4-di-O-benzyl-3,6-di-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl)-α-D-mannopyranoside
  参考文献：
  名称：

  Synthesis of a nonasaccharide with two lewis x trisaccharides anchored onto a branched trimannoside

  摘要：

  Double condensation of phenyl 3,4,6-tri-O-benzyl-2-O-[6-O-benzyl-2-deoxy-2-phthalimido-4-O-(2 ,3,4,6-tetra-O-benzoyl-beta-D-galactopyranosyl)-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-beta-D-glucopyranosyl]- 1-thio-alpha-D-mannopyranoside 31 with methyl 2,4-di-O-benzyl-beta-D-mannopyranoside 35, in the presence of N-iodosuccinimide/trifluoromethane-sulfonic acid, gave the protected nonasaccharide 36 in 60% yield. Conventional deprotection gave the nonasaccharide 1, in which two Lewis x trisaccharides are anchored onto a branched trimannoside.

  DOI：

  10.1016/0957-4166(95)00146-g

文献信息

• Nucleofuge Generating Glycosidations by the Remote Activation of Hydroxybenzotriazolyl Glycosides
  作者：Mahesh Neralkar、Bijoyananda Mishra、Srinivas Hotha

  DOI：10.1021/acs.joc.7b02027

  日期：2017.11.3

  by the extrusion of the oxocarbenium ion that was attacked by the glycosyl acceptor. Further, equilibration of the zwitterionic benzotriazolyl species makes the leaving group noncompetitive and generates the nucleofuge that has been reconverted to the glycosyl donor. The reaction is mild, high yielding, fast and suitable for donors containing both C2-ethers and C2-esters as well. The regenerative-donor

  羟基苯并三唑因其增加的反应性而通常用于肽化学中，以减少外消旋作用。在本文中，鉴定出非常稳定的羟基苯并三唑基葡糖苷可以进行糖苷化。假设该反应通过Tf 2进行远程激活在HOBt的N3位点为O，接着是被糖基受体攻击的氧碳鎓离子的挤出。此外，两性离子苯并三唑基物质的平衡使离去基团失去竞争性，并产生已被重新转化为糖基供体的核沉子。该反应温和，高产率，快速并且适合于同时含有C2-醚和C2-酯的供体。再生供体糖苷化策略是有前途的，因为它使我们能够再生糖基供体以供进一步利用。通过成功合成HIV1-gp120复合物的支链五聚甘露聚糖核心，证明了该方法在寡糖合成中的实用性。
• One pot/two donors/one diol give one differentiated trisaccharide: powerful evidence for reciprocal donor–acceptor selectivity (RDAS)
  作者：Bert Fraser-Reid、J. Cristóbal López、K. V. Radhakrishnan、M. V. Nandakumar、Ana M. Gómez、Clara Uriel

  DOI：10.1039/b206598c

  日期：——

  Three component, one-pot reactions involving equimolar amounts of the acceptor diol and both armed and disarmed donors presented simultaneously, produce a single double-differential glycosidation product; this phenomenon provides evidence for Reciprocal Donor Acceptor Selectivity (RDAS).

  由等摩尔量的受体二元醇和同时出现的武装和非武装供体组成的三组分一锅反应会产生单一的双差糖化产物；这一现象为互作供体受体选择性（RDAS）提供了证据。
• A study of n-pentenylorthoesters having manno, gluco and galacto configurations in regioselective glycosylations
  作者：K.N. Jayaprakash、Bert Fraser-Reid

  DOI：10.1016/j.carres.2006.09.022

  日期：2007.2

  Kochetkov's extensive investigations of glycosyl orthoester and their analogs as glycosyl donors revealed that the alkyl derivatives were plagued by competition between the departing alcohol and the incoming acceptor. n-Pentenyl orthoesters (NPOEs) obviate competition by sequestering the departing pentenyl alcohol as a 2-halomethyl tetrahydrofuran. Exquisitely regioselective glycosidations of diol acceptors can be carried out with NPOEs triggered specifically with Yb(OTf)(3)/NIS. However with Sc(OTf)(3), double glycosidation is the major reaction. manno, gluco and galacto NPOEs have been investigated. The latter two, which require a different experimental procedure for the manno counterpart, also give an excellent regioselectivity with Yb(OTf)(3), but the yields are much lower than with manno. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of a nonasaccharide with two lewis x trisaccharides anchored onto a branched trimannoside
  作者：Yong-Min Zhang、Annie Brodzky、Pierre Sinaÿ、Guillaume Saint-Marcoux、Bruno Perly

  DOI：10.1016/0957-4166(95)00146-g

  日期：1995.5

  Double condensation of phenyl 3,4,6-tri-O-benzyl-2-O-[6-O-benzyl-2-deoxy-2-phthalimido-4-O-(2 ,3,4,6-tetra-O-benzoyl-beta-D-galactopyranosyl)-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-beta-D-glucopyranosyl]- 1-thio-alpha-D-mannopyranoside 31 with methyl 2,4-di-O-benzyl-beta-D-mannopyranoside 35, in the presence of N-iodosuccinimide/trifluoromethane-sulfonic acid, gave the protected nonasaccharide 36 in 60% yield. Conventional deprotection gave the nonasaccharide 1, in which two Lewis x trisaccharides are anchored onto a branched trimannoside.
• N-Heterocyclic silylene/germylene ligands in Au(<scp>i</scp>) catalysis
  作者：Nasrina Parvin、Bijoyananda Mishra、Anjana George、Mahesh Neralkar、Jabed Hossain、Pattiyil Parameswaran、Srinivas Hotha、Shabana Khan

  DOI：10.1039/d0cc03156a

  日期：——

  Cationic Au(I) complexes (2, 5 and 8) supported by N-heterocyclic carbene, silylene and germylene ligands were prepared and their potential as catalysts in glycosidation chemistry has been evaluated. Insights into the mechanism are provided using DFT studies. Practical application of them as catalysts was achieved by the synthesis of the branched pentamannan core of the HIV-gp120 envelope under mild

  制备了由N-杂环卡宾，亚甲硅烷基和亚二甲苯基配体支撑的阳离子Au（I）配合物（2、5和8），并评估了它们在糖苷化学中作为催化剂的潜力。使用DFT研究提供了对该机制的见解。通过在温和条件下合成HIV-gp120包膜的支链五聚甘露聚糖核心，可以将它们实际用作催化剂。