methyl 2,6-di-O-benzyl-5-C-methoxy-β-D-galactopyranoside | 134039-09-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,6-di-O-benzyl-5-C-methoxy-β-D-galactopyranoside
• 英文别名: (2R,3R,4S,5R,6R)-2,6-dimethoxy-5-phenylmethoxy-2-(phenylmethoxymethyl)oxane-3,4-diol
• CAS: 134039-09-1
• 化学式: C₂₂H₂₈O₇
• 分子量: 404.46
• InChiKey: AFXTUILJCXPQFS-ZGJYDULXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  86.6
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2,6-di-O-benzyl-5-C-methoxy-β-D-galactopyranoside 在 palladium dihydroxide Novozym N₄₃₅ lipase 、 氢气 、 对甲苯磺酸 作用下， 以 乙酸乙酯 为溶剂， 反应 198.0h， 生成 methyl 6-O-acetyl-3,4-O-isopropylidene-5-C-methoxy-β-D-galactopyranoside
  参考文献：
  名称：

  The First Synthesis of aRibo-Hexos-5-Ulose: the L-Enantiomer

  摘要：

  The title compound, previously unreported in either enantioform, and its 2,6-di-O-benzyl derivative have been synthesized through a stereocontrolled epimerization at C-2 of 6-O-protected methyl 3,4-O-isopropylidene-5-C-methoxy-beta-D-galactopyranosides The epimerization, performed through a high yielding sequence of oxidation-reduction owing to the cooperative role of the equatorial C-l aglycon and the steric hindrance of the isopropylidene group, turned out to be completely diastereoselective. Whereas the unprotected L-ribo-hexos-5-ulose exists, as proved by NMR in D2O, in five main tautomeric forms in a ratio of about 4:2:2:1:1, only two anomeric 1,4-furanosic forms are present at equilibrium in its 2,6-di-O-benzyl derivative, in ratios ranging from 10:1 to 7:3, depending on the prevalence of D2O or CD3CN in the solvent mixture.

  DOI：

  10.1080/07328309908544053
• 作为产物：
  描述：

  methyl 2,6-di-O-benzyl-4-deoxy-α-L-threo-hex-4-enopyranoside 在 氢气 、 间氯过氧苯甲酸 作用下， 生成 methyl 2,6-di-O-benzyl-5-C-methoxy-β-D-galactopyranoside
  参考文献：
  名称：

  一种简单的立体定向途径，可制得5-C-烷氧基-D-吡喃半乳糖苷和L-阿拉伯糖-己糖-5-uloses

  摘要：

  可以容易地转化为L-阿拉伯糖-己糖-5-uloses的5-C-烷氧基-β-D-吡喃半乳糖苷可以由β-D-吡喃半乳糖苷在中间体4-脱氧-α的醇溶剂中通过过氧酸氧化制备-L-苏式-hex-4-enopyranosides。

  DOI：

  10.1016/s0040-4039(00)92130-0

文献信息

• A new method for the synthesis of carba-sugar enones (gabosines) using a mercury(II)-mediated opening of 4,5-cyclopropanated pyranosides as the key-step
  作者：Antonino Corsaro、Venerando Pistarà、Giorgio Catelani、Felicia D’Andrea、Roberto Adamo、Maria Assunta Chiacchio

  DOI：10.1016/j.tetlet.2006.07.023

  日期：2006.9

  The stereoselective transformation of the cyclopropyl derivative 2, stereoselectively obtained with the Simmons–Smith reaction of methyl 2,6-di-O-benzyl-α-l-threo-hex-4-enopyranoside (1), into gabosines and deoxy-carbahexoses is described. The treatment of 2 with mercuric trifluoroacetate in dry methanol gives the organomercuric chloride 3, which by demercuration with lithium aluminum hydride affords

  环丙基衍生物2的立体选择性转化是通过甲基2,6-二-O-苄基-α-l-苏-hex-4- enopyranoside（1）的Simmons-Smith反应立体选择性地转化为葡糖苷和脱氧氨基甲酸酯。描述。在干燥的甲醇中用三氟乙酸汞处理2，得到有机汞氯化物3，通过与氢化铝锂脱汞，得到4 C-脱氧-4-甲基-1,5-双-糖苷4。4的酸水解产生两个非对映异构体2-甲基-环己二-2-烯酮6和7的混合物，催化还原为糖10和11。所有分离的化合物的结构和立体化学均通过1D和2D NMR实验确定。
• Barili, Pier Luigi; Berti, Giancarlo; Catelani, Giorgio, Gazzetta Chimica Italiana, 1992, vol. 122, # 4, p. 135 - 142
  作者：Barili, Pier Luigi、Berti, Giancarlo、Catelani, Giorgio、D'Andrea, Felicia

  DOI：——

  日期：——
• A new route to d-xylo-hexos-5-ulose and some of its selectively protected derivatives from d-galactose
  作者：Pier Lugi Barili、Giancarlo Berti、Giorgio Catelani、Felicia D'Andrea、Francesco De Rensis

  DOI：10.1016/s0040-4020(97)00536-x

  日期：1997.6

  A new approach to D-xylo-hexos-5-ulose, a useful synthetic intermediate, is described, starting from methyl beta-D-galactopyranoside and involving as the key step an epoxidation/methanolysis of 3-O-protected methyl 2,6-di-O-benzyl-4-deoxy-alpha-L-threo-hex-4-enopyranosides, to produce bis-glycosides of the parent dicarbonylic sugar, which can be obtained free or selectively protected through hydrogenolytic and/or hydrolytic procedures. The diastereo- and regioselectivity of the epoxidation and solvolysis steps are investigated and tentatively interpreted, and new products characterized by NMR techniques, (C) 1997 Elsevier Science Ltd.
• A new stereoselective approach to a selectively protected derivative of d-pinitol and its evaluation as α-l-rhamnopyranose mimetic
  作者：Giorgio Catelani、Felicia D’Andrea、Alessio Griselli、Lorenzo Guazzelli、Laura Legnani、Lucio Toma

  DOI：10.1016/j.tetlet.2008.05.040

  日期：2008.7

  The synthesis of 3,5-di-O-benzyl-D-pinitol has been stereoselectively accomplished through intramolecular aldolization of 2,6-di-O-benzyl-4-O-methyl-L-lyxo-hexos-5-ulose followed by reduction with NaBH(OAc)(3). Computational analysis [DFT calculations at the B3LYP/6-31G(d) level] suggests that D-pinitol in water largely prefers the conformation corresponding to the (1)C4 one of a alpha-L-rhamnopyranoside unit, being thus a good candidate for its mimicking. (c) 2008 Elsevier Ltd. All rights reserved.
• Preparation of L-<i>Lyxo</i>-Hexos-5-Ulose Through C-3 Epimerization of Bis-Glycopyranosides of L-<i>Arabino</i>-Hexos-5-Ulose¹
  作者：Pier Luigi Barili、Giancarlo Berti、Giorgio Catelani、Felicia D'Andrea、Francesco De Rensis、Giampaolo Goracci

  DOI：10.1080/07328309808001891

  日期：1998.11

  The unreported title compound and its 2,6-di-O-benzyl derivative have been prepared from methyl beta-D-galactopyranoside through a sequence involving the bis-glycoside methyl 2,6-di-O-benzyl-5-C-methoxy-beta-D-galactopyranoside 8, the precursor of L-arabino-hexos-5-ulose, that was converted to the L-lyxo series by inversion at C-3. The inversion was achieved in acceptable yields by selective triflation, followed by displacement with benzoate, and by an oxidation/reduction sequence. Whereas 2,5-di-O-benzyl-L-lyxo-hexos-5-ulose exists entirely as a mixture of the two anomeric 1,4-furanosic forms, the unprotected hexos-5-ulose involves at equilibrium in CD3CN/D2O at least eight tautomers, one of which is predominant.