3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-galacto-2-heptulopyranose | 271243-80-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-galacto-2-heptulopyranose
• 英文别名: (2R,3R,4S,5S,6R)-2-(dimethoxyphosphorylmethyl)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol
• CAS: 271243-80-2
• 化学式: C₃₇H₄₃O₉P
• 分子量: 662.717
• InChiKey: IWDFDXKOAWXJTN-AESTUDHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  47
• 可旋转键数：
  17
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-galacto-2-heptulopyranose 在 palladium on activated charcoal 吡啶 、 氢气 、 三氟乙酸酐 作用下， 以 甲醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 67.0h， 生成 (Z)-3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-1-dimethoxyphosphoryl-D-galacto-hept-1-enitol
  参考文献：
  名称：

  新型UDP-Glycal衍生物作为UDP-GlcNAc 2-表异构酶的过渡态类似抑制剂

  摘要：

  UDP-GlcNAc 2-epimerase催化将唾液酸生物合成过程中的第一步从UDP-GlcNAc到ManNAc的“表位化”。在本文中，我们报告了该酶基于过渡态抑制剂的合成。为了模拟该反应的假定的第一过渡态（TS 1），我们设计并合成了新型UDP-外糖基衍生物1-4。我们在此还报告了5和6的合成，2-乙酰氨基葡糖的第一个C-糖苷衍生物以及酮苷7和8的合成，它们分别被设计为双底物类似物和双产物类似物，以模拟通过假定的第二过渡态TS 2进行反应的第二步。

  DOI：

  10.1021/jo0353029
• 作为产物：
  描述：

  2,3,4,6-四-O-(苯基甲基)-D-半乳糖酸 D-内酯 、 甲基膦酸二甲酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.33h， 以72%的产率得到3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-galacto-2-heptulopyranose
  参考文献：
  名称：

  Stereoselective synthesis of C-glycosylphosphonates from their ketols. Reconsideration of an abandoned route

  摘要：

  Isosteric phosphonate analogues of glycosyl 1-phosphates have been obtained by addition of LiCH2P(O)(OMe)(2) to glyconolactones followed by Et3SiH-TMSOTf reductive dehydroxylation of the resultant ketols. The compounds prepared include four beta-linked pyranose derivatives (D-galacto, 2-azido-2-deoxy-D-galacto, D-gluco, D-manno) and one beta-linked furanose derivative (D-manno). In the latter case the ketol was activated as its 2-acetate. In agreement with an observation in another laboratory, the dehydroxylation of a model ketol phosphonate failed with the use of Et3SiH-BF3. Et2O. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00477-2

文献信息

• Synthesis of Spirocyclic Cyclopropyl Glycosyl-1-phosphate Analogues
  作者：Jun Cao、Stéphane P. Vincent

  DOI：10.1021/acs.orglett.2c01422

  日期：2022.6.17

  A general methodology allowing the preparation of phosphonylated 1-spirocyclopropyl analogues of glycosyl-1-phosphates is reported. The scope of this reaction has been assessed using various exo-glycals easily obtained from the corresponding pyranoses and furanoses. The cyclopropanation was found to be stereospecific, and the cis/trans selectivity only depends on the E/Z configuration of the starting

  报道了一种允许制备 1-磷酸糖基 1-螺环丙基类似物的通用方法。已经使用从相应的吡喃糖和呋喃糖容易获得的各种外聚糖来评估该反应的范围。发现环丙烷化是立体特异性的，顺式/反式选择性仅取决于起始外-糖基的E / Z构型。螺环丙基核糖-1-膦酸酯的四种可能异构体因此可以以受控方式制备、保护和去保护。
• Stereoselective synthesis of C-glycosylphosphonates from their ketols. Reconsideration of an abandoned route
  作者：Alessandro Dondoni、Alberto Marra、Claudia Pasti

  DOI：10.1016/s0957-4166(99)00477-2

  日期：2000.1

  Isosteric phosphonate analogues of glycosyl 1-phosphates have been obtained by addition of LiCH2P(O)(OMe)(2) to glyconolactones followed by Et3SiH-TMSOTf reductive dehydroxylation of the resultant ketols. The compounds prepared include four beta-linked pyranose derivatives (D-galacto, 2-azido-2-deoxy-D-galacto, D-gluco, D-manno) and one beta-linked furanose derivative (D-manno). In the latter case the ketol was activated as its 2-acetate. In agreement with an observation in another laboratory, the dehydroxylation of a model ketol phosphonate failed with the use of Et3SiH-BF3. Et2O. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Novel UDP-Glycal Derivatives as Transition State Analogue Inhibitors of UDP-GlcNAc 2-Epimerase
  作者：Florian Stolz、Martin Reiner、Astrid Blume、Werner Reutter、Richard R. Schmidt

  DOI：10.1021/jo0353029

  日期：2004.2.1

  the first step in the biosynthesis of sialic acids, is catalyzed by UDP-GlcNAc 2-epimerase. In this paper we report the synthesis of transition state based inhibitors of this enzyme. To mimic the assumed first transition state of this reaction (TS 1), we designed and synthesized the novel UDP-exo-glycal derivatives 1−4. We also report herein the synthesis of 5 and 6, the first C-glycosidic derivatives

  UDP-GlcNAc 2-epimerase催化将唾液酸生物合成过程中的第一步从UDP-GlcNAc到ManNAc的“表位化”。在本文中，我们报告了该酶基于过渡态抑制剂的合成。为了模拟该反应的假定的第一过渡态（TS 1），我们设计并合成了新型UDP-外糖基衍生物1-4。我们在此还报告了5和6的合成，2-乙酰氨基葡糖的第一个C-糖苷衍生物以及酮苷7和8的合成，它们分别被设计为双底物类似物和双产物类似物，以模拟通过假定的第二过渡态TS 2进行反应的第二步。