3,7-anhydro-4,5,6,8-tetra-O-benzyl-2-deoxy-D-galacto-oct-1-ethoxycarbonyl-2-Z-enitol | 214771-14-9

• 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: 3,7-anhydro-4,5,6,8-tetra-O-benzyl-2-deoxy-D-galacto-oct-1-ethoxycarbonyl-2-Z-enitol
• 英文别名: (1(1')-Z)-2,3,4,6-tetra-O-benzyl-1-deoxy-1-(ethoxycarbonyl)methylidene-D-galactopyranose；2,3,4,6-tetra-O-benzyl-1-(ethoxycarbonyl)methyl-D-galactopyranose；ethyl (2Z)-2-[(3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ylidene]acetate
• CAS: 214771-14-9
• 化学式: C₃₈H₄₀O₇
• 分子量: 608.731
• InChiKey: VJWCXAYHDZOQFF-NBPJLVNISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  45
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,7-anhydro-4,5,6,8-tetra-O-benzyl-2-deoxy-D-galacto-oct-1-ethoxycarbonyl-2-Z-enitol 在 吡啶 、 4-二甲氨基吡啶 、 四氧化锇 、 N-甲基吲哚酮 作用下， 以 水 、 丙酮 为溶剂， 反应 30.0h， 生成 ethyl acetoxy(1-acetoxy-2,3,4,6-tetra-O-benzyl-D-galactopyranosyl)ethanoate
  参考文献：
  名称：

  Alkylidenation of Sugar Lactones and Further Transformation toC-Glycosides

  摘要：

  The Wittig reaction of (carbethoxymethylene)triphenylphosphorane with perbenzylated sugar delta-lactones and their 2-acetamido-2-deoxy derivatives is described. It is shown that this olefination occurred readily with the galacto and gluco derivatives, leading stereoselectively to Z-C-glycosylidenes in good yields. However, the same reaction with the perbenzylated 2-deoxy-D-arabino-hexono-1,5-lactone and the mannonolactones worked poorly. Reduction over Pd/C followed by acetylation of the obtained C-glycosylidenes led stereoselectively to peracetylated beta-C-glycosides and amino beta-C-glycosides. The olefin function could also be reduced selectively by Raney nickel or NiCl2/NaBH4, affording the perbenzylated C-glycosides and amino beta-C-glycosides. Other transformation of the enol ether function is also reported.

  DOI：

  10.1080/07328309908544013
• 作为产物：
  描述：

  ethyl 2-deoxy-4,5,6,8-tetra-O-benzyl-α-D-galacto-3,7-pyranoso-3-octulosonate 在 吡啶 、 三氟乙酸酐 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以81%的产率得到3,7-anhydro-4,5,6,8-tetra-O-benzyl-2-deoxy-D-galacto-oct-1-ethoxycarbonyl-2-Z-enitol
  参考文献：
  名称：

  立体化学在外糖的合成和反应中。

  摘要：

  探索了两种一般方法来立体选择性合成外糖。一种方法利用亲核加成葡萄糖，半乳糖和甘露糖型的完全保护的糖内酯，随后进行脱水，以得到具有（Z）构型的期望的外糖。另一种方法以立体选择性方式进行C-糖苷的硒化。随后的亚硒酸盐消除也提供了（Z）-外糖。制备的葡萄糖型或甘露型的外糖共轭酯与烯丙醇反应，仅得到α-异头物。

  DOI：

  10.1021/jo0255227

文献信息

• Stereoselective Synthesis of <i>C</i>,<i>C</i>-Glycosides from <i>exo</i>-Glycals Enabled by Iron-Mediated Hydrogen Atom Transfer
  作者：Damien Tardieu、Marine Desnoyers、Claire Laye、Damien Hazelard、Nicolas Kern、Philippe Compain

  DOI：10.1021/acs.orglett.9b02496

  日期：2019.9.20

  We describe herein a convenient strategy for the construction of C,C-glycoside building blocks via the intermediacy of tertiary pseudoanomeric radicals. Application of an iron-mediated hydrogen atom transfer/Michael–Giese coupling enables the anomeric quaternization of readily available exo-glycals with good to complete stereocontrol in the pyranose and furanose series. Carefully optimized conditions

  我们在本文中描述了通过叔假异构基团的中间体构建C，C-糖苷结构单元的方便策略。铁介导的氢原子转移/ Michael–Giese偶联的应用使得易得的外糖的异头季铵化反应能够很好地完成吡喃糖和呋喃糖系列的立体控制。精心优化的条件允许使用具有挑战性的易取代的三取代衍生物，使其易于进一步精制成稳定的新糖缀合物。还讨论了直接C-二糖合成的初步结果。
• Stereocontrolled synthesis of β-C-glycosides and amino β-C-glycosides by Wittig olefination of perbenzylated glyconolactones derivatives
  作者：Adeline Molina、Stanislas Czernecki、Juan Xie

  DOI：10.1016/s0040-4039(98)01627-x

  日期：1998.10

  Wittig olefination of perbenzylated glyconolactones afforded stereoselectively the Z-C-glycosylidenes which were transformed to the corresponding beta-C-glycosides and amino beta-C glycosides by hydrogenation followed by acetylation. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Inter- and intramolecular alcohol additions to exo -glycals
  作者：Chuan-Fa Chang、Wen-Bin Yang、Che-Chien Chang、Chun-Hung Lin

  DOI：10.1016/s0040-4039(02)01473-9

  日期：2002.9

  Various exo-glycals were explored for the glycosidic bond formation and synthesis of spiroacetals in a stereoselcctive manner. The former reaction was an intermolecular alcohol addition to give the S new stereogenic center, resulting from the nucleophilic attack from the bottom face of the sugar ring. The latter one was carried Out by the hydroboration of a sugar diene, followed by a Subsequent acid workup. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Stereochemistry in the Synthesis and Reaction of <i>e</i><i>xo</i>-Glycals
  作者：Wen-Bin Yang、Yu-Ying Yang、Yu-Feng Gu、Shwu-Huey Wang、Che-Chien Chang、Chun-Hung Lin

  DOI：10.1021/jo0255227

  日期：2002.5.1

  Two general methods are explored for the stereoselective synthesis of exo-glycals. One method utilizes a nucleophilic addition of fully protected sugar lactones of gluco-, galacto-, and manno-types, followed by the subsequent dehydration, to give the desired exo-glycals with (Z)-configuration. The other method proceeds with selenylation of C-glycosides in a stereoselective manner. The subsequent selenoxide

  探索了两种一般方法来立体选择性合成外糖。一种方法利用亲核加成葡萄糖，半乳糖和甘露糖型的完全保护的糖内酯，随后进行脱水，以得到具有（Z）构型的期望的外糖。另一种方法以立体选择性方式进行C-糖苷的硒化。随后的亚硒酸盐消除也提供了（Z）-外糖。制备的葡萄糖型或甘露型的外糖共轭酯与烯丙醇反应，仅得到α-异头物。
• Alkylidenation of Sugar Lactones and Further Transformation to<i>C</i>-Glycosides
  作者：Juan Xie、Adeline Molina、Stanislas Czernecki

  DOI：10.1080/07328309908544013

  日期：1999.1

  The Wittig reaction of (carbethoxymethylene)triphenylphosphorane with perbenzylated sugar delta-lactones and their 2-acetamido-2-deoxy derivatives is described. It is shown that this olefination occurred readily with the galacto and gluco derivatives, leading stereoselectively to Z-C-glycosylidenes in good yields. However, the same reaction with the perbenzylated 2-deoxy-D-arabino-hexono-1,5-lactone and the mannonolactones worked poorly. Reduction over Pd/C followed by acetylation of the obtained C-glycosylidenes led stereoselectively to peracetylated beta-C-glycosides and amino beta-C-glycosides. The olefin function could also be reduced selectively by Raney nickel or NiCl2/NaBH4, affording the perbenzylated C-glycosides and amino beta-C-glycosides. Other transformation of the enol ether function is also reported.