1,4-anhydro-2,3,6-tri-O-benzyl-β-D-galactopyranose | 95217-08-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,4-anhydro-2,3,6-tri-O-benzyl-β-D-galactopyranose
• 英文别名: tri-O-benzyl-1,4-anhydrogalactopyranose；(1S,3R,4S,5S,6R)-5,6-bis(phenylmethoxy)-3-(phenylmethoxymethyl)-2,7-dioxabicyclo[2.2.1]heptane
• CAS: 95217-08-6
• 化学式: C₂₇H₂₈O₅
• 分子量: 432.516
• InChiKey: XECSHKNUIYGKGY-KQZFZZGISA-N

物化性质

• 沸点：
  560.3±50.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,4-anhydro-2,3,6-tri-O-benzyl-β-D-galactopyranose 在 三氟甲磺酸三甲基硅酯 作用下， 生成 (1R)-1-[(2S,3R,3aS,9bR)-3-phenylmethoxy-3,3a,5,9b-tetrahydro-2H-furo[3,2-c]isochromen-2-yl]-2-phenylmethoxyethanol
  参考文献：
  名称：

  通过1,4-脱水吡喃半乳糖衍生物的区域选择性开环合成半乳糖呋喃糖苷：前所未有的酶反应的可能的化学模型。

  摘要：

  DOI：

  10.1002/1099-0690(200012)2000:21<4125::aid-ejoc4125>3.0.co;2-l
• 作为产物：
  描述：

  在 N-碘代丁二酰亚胺 作用下， 以49%的产率得到1,4-anhydro-2,3,6-tri-O-benzyl-β-D-galactopyranose
  参考文献：
  名称：

  1,4-Anhydrogalactopyranose is not an intermediate of the mutase catalyzed UDP-galactopyranose/furanose interconversion

  摘要：

  UDP-galactopyranose mutase (UGM) catalyzes the isomerization of UDP-galactopyranose (UDP-Galp) into UDP-galactofuranose (UDP-Galf), an essential step of the mycobacterial cell wall biosynthesis. The first mechanistic assumption proposed in the literature was the involvement of 1,4-anhydrogalactose 1 as intermediate of this ring contraction. To confirm or rule out this hypothesis, we synthesized 1 and engaged it in reactions with UGM. The expected formations of UDP-Galf and UDP-Galp were never observed, thus showing that 1 is not, in fact, a low energy intermediate of this enzymatic contraction. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2005.11.106

文献信息

• The UDP-Galp mutase catalyzed isomerization: synthesis and evaluation of 1,4-anhydro-β-d-galactopyranose and its [2.2.2] methylene homologue
  作者：Ali Sadeghi-Khomami、Tatiana J. Forcada、Claire Wilson、David A. R. Sanders、Neil R. Thomas

  DOI：10.1039/b917409e

  日期：——

  The synthesis of 1,4-anhydro-β-D-galactopyranose (1,5-anhydro-α-D-galactofuranose), a proposed intermediate in the ring contraction isomerisation catalyzed by UDP-galactopyranose mutase, together with its [2.2.2] bicyclic methylene homologue, synthesised as a possible competitive inhibitor or alternative substrate, are reported. Neither compound was found to be an inhibitor or substrate for UDP-galactopyranose mutase from Klebsiella pneumoniae.

  报道了1,4-脱水-β-D-半乳糖吡喃糖（1,5-脱水-α-D-半乳糖呋喃糖）的合成，该化合物被提议作为UDP-半乳糖吡喃糖变位酶催化的环收缩异构化过程中的中间体，此外还合成了其[2.2.2]双环亚甲基同系物，作为可能的竞争抑制剂或替代底物。结果发现，这两种化合物均未被发现是来自肺炎克雷伯菌的UDP-半乳糖吡喃糖变位酶的抑制剂或底物。
• Synthesis of Galactofuranosides by Regioselective Ring Opening of a 1,4-Anhydrogalactopyranose Derivative: A Possible Chemical Model for an Unprecedented Enzymatic Reaction
  作者：José Kovensky、Pierre Sinaÿ

  DOI：10.1002/1099-0690(200011)2000:21<3523::aid-ejoc3523>3.0.co;2-c

  日期：2000.11

  The known 1,4-anhydro-2,3,6-tri-O-benzyl-β-D-galactopyranose (1) has been regioselectively ring-opened using a variety of nucleophiles under acidic conditions to exclusively afford furanosides.

  已知的 1,4-脱水-2,3,6-三-O-苄基-β-D-吡喃半乳糖 (1) 已在酸性条件下使用各种亲核试剂进行区域选择性开环，以专门提供呋喃糖苷。
• Synthesis and Reactions of 1,4-Anhydrogalactopyranose and 1,4-Anhydroarabinose - Steric and Electronic Limitations
  作者：Toshiki Nokami、Daniel B. Werz、Peter H. Seeberger

  DOI：10.1002/hlca.200590224

  日期：2005.11

  Scope and limitations of 1,4-anhydro sugars as precursors of glycofuranosyl building blocks are described. The experiments revealed that the choice of the substituents is very important for an efficient preparation as well as a successful ring-opening reaction of 1,4-anhydro sugars. DFT Calculations suggest that selective protonation of 1,4-anhydro sugars is the key to the selective ring opening in

  描述了1，4-脱水糖作为呋喃呋喃糖基结构单元前体的范围和局限性。实验表明，取代基的选择对于有效制备以及成功地进行1,4-脱水糖的开环反应非常重要。DFT计算表明，1,4-脱水糖的选择性质子化是仅提供呋喃糖苷的选择性开环的关键。
• Facile Preparation of 1,6-Anhydrohexoses using Solvent Effects and a Catalytic Amount of a Lewis Acid.
  作者：Per-Mikael Åberg、Beat Ernst、Erik De Clercq、Graciela Andrei、Robert Snoeck、Jan Balzarini、Bengt Fransson、Ulf Ragnarsson、George W. Francis

  DOI：10.3891/acta.chem.scand.48-0228

  日期：——

  Refluxing solutions of monosaccharides, unprotected at the 6-position and carrying O-methyl, S-ethyl, O-acetyl and OH-groups at the anomeric center, in acetonitrile containing a catalytic amount of a Lewis acid (O.1-0.4 equiv.) yielded 1,6-anhydrohexopyranoses in good to high yields. Best results were obtained with methyl 2,3,4-tri-O-dideuteriobenzyl-alpha-D-glycosides (87-91%). Dideuteriobenzyl protective

  在6位无保护并在端基中心带有O-甲基，S-乙基，O-乙酰基和OH-基团的单糖的回流溶液，在含有催化量路易斯酸（O.1-0.4当量。）以良好至高收率得到1,6-脱水己基吡喃糖。甲基2,3,4-三-O-二氘代苄基-α-D-糖苷（87-91％）获得了最佳结果。使用二异氘苄基保护基来促进NMR谱图的解释。
• 1,4-Anhydrogalactopyranose is not an intermediate of the mutase catalyzed UDP-galactopyranose/furanose interconversion
  作者：Audrey Caravano、Pierre Sinaÿ、Stéphane P. Vincent

  DOI：10.1016/j.bmcl.2005.11.106

  日期：2006.3

  UDP-galactopyranose mutase (UGM) catalyzes the isomerization of UDP-galactopyranose (UDP-Galp) into UDP-galactofuranose (UDP-Galf), an essential step of the mycobacterial cell wall biosynthesis. The first mechanistic assumption proposed in the literature was the involvement of 1,4-anhydrogalactose 1 as intermediate of this ring contraction. To confirm or rule out this hypothesis, we synthesized 1 and engaged it in reactions with UGM. The expected formations of UDP-Galf and UDP-Galp were never observed, thus showing that 1 is not, in fact, a low energy intermediate of this enzymatic contraction. (C) 2005 Elsevier Ltd. All rights reserved.