methyl-2,3,4-tetra-O-benzyl-L-glycero-α-D-manno-heptopyranoside | 122588-51-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-2,3,4-tetra-O-benzyl-L-glycero-α-D-manno-heptopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzyl-L-glycero-α-D-manno-heptopyranoside；methyl 2,3,4-O-tribenzyl-L-glycero-α-D-manno-heptopyranoside；methyl 2,3,4-tri-O-benzyl-glycero-α-D-manno-heptopyranoside；(1S)-1-[(2R,3S,4S,5S,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]ethane-1,2-diol
• CAS: 122588-51-6
• 化学式: C₂₉H₃₄O₇
• 分子量: 494.585
• InChiKey: KJQCVAVXJPYFDH-QJFVUISJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 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-2,3,4-tetra-O-benzyl-L-glycero-α-D-manno-heptopyranoside 生成 methyl 2,3:6,7-di-O-isopropylidene-L-glycero-α-D-manno-heptopyranoside
  参考文献：
  名称：

  一种通用的新型高度立体选择性的方法，用于合成l-甘油-d-甘露聚糖-七吡喃糖苷

  摘要：

  （苯基二甲基）甲硅烷基甲基镁氯化物与苄基2,3,4-三-O-苄基-α-D-甘露聚糖-己二醛-1,5-吡喃糖苷的反应得到相应的L-甘油-D-甘露聚糖-加成产物，其具有C-7为苯基二甲基甲硅烷基（PDMSi）。后者的甲硅烷基化合物在OH-6处的苄基化和糖基化作用下均能幸存下来，并且PDMSi基团可以被掩盖，从而保持整体构型，从而获得游离羟基。

  DOI：

  10.1016/s0040-4039(00)95167-0
• 作为产物：
  描述：

  methyl 6-deoxy-2,3,4-tri-O-benzyl-α-D-gluco-hepto-1,7-dialdopyranoside 在 sodium tetrahydroborate 、 copper(II) sulfate 、 L-脯氨酸 作用下， 以 甲醇 、 乙醇 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.08h， 生成 methyl-2,3,4-tetra-O-benzyl-L-glycero-α-D-manno-heptopyranoside
  参考文献：
  名称：

  General Homologation Strategy for Synthesis of l-glycero- and d-glycero-Heptopyranoses

  摘要：

  A general and stereospecific homologation strategy for the synthesis of heptopyranosides is reported. The strategy employs the Wittig olefination and proline-catalyzed a-aminoxylation to achieve one carbon elongation and stereoselective hydroxylation at the C6 position, respectively. The l-glycero- and d-glycero-heptopyranosides can be obtained with nearly perfect stereoselectivity. Further study reveals the difference in the chemical shift of the C6 proton of l/d-glycero-heptopyranosyl diastereomers, which is found to be useful for assignment of the configuration of heptopyranosides.

  DOI：

  10.1021/acs.orglett.5b02620

文献信息

• Multigram-scale synthesis of l,d-heptoside using a Fleming-Tamao oxidation promoted by mercuric trifluoroacetate
  作者：Tianlei Li、Abdellatif Tikad、Maxime Durka、Weidong Pan、Stéphane P. Vincent

  DOI：10.1016/j.carres.2016.07.010

  日期：2016.9

  efficient multigram-scale synthesis of methyl 2,3,4,6-tetra-O-benzyl-l-glycero-α-d-manno-heptopyranoside from methyl 2,3,4-tri-O-benzyl-α-d-mannopyranoside is reported. It involves a sequence of Swern oxidation, Grignard addition and Fleming-Tamao reactions. The resulting scaffold was used as a precursor to design a small library of clickable l-heptosides. This study shows that the use of mercuric bistrifluoroacetate

  由甲基2,3,4-三-O-苄基-α-d高效合成多克级的甲基2,3,4,6-四-O-苄基-1-甘油-α-d-甘露庚基吡喃糖苷报道了-甘露吡喃糖苷。它涉及一系列的Swern氧化，格利雅（Grignard）加成反应和Fleming-Tamao反应。所得支架用作设计可点击的l-庚糖苷小文库的前体。这项研究表明，需要使用双三氟乙酸汞来加速和清洁地进行Fleming-Tamao氧化，且无副反应。
• Diastereoselectivity in the synthesis of <scp>D</scp>-glycero-<scp>D</scp>-aldoheptoses by 2-trimethylsilylthiazole homologation from hexodialdo-1,5-pyranose derivatives
  作者：Naveen K. Khare、Ramesh K. Sood、Gerald O. Aspinall

  DOI：10.1139/v94-036

  日期：1994.1.1

  An exploration of the synthesis of D-glycero-D-altro-heptose, a constitutent of O antigen chains in lipopolysaccharides from Campylobacter jejuni serotypes O:23 and O:36 led to a study of the 2-trimethylsilylthiazole homologation procedure for heptose synthesis. In contrast to the diastereoselective formation of a 1,2:3,4-di-O-isopropylidene-D-glycero-α-D-galacto-heptopyranose derivative from 1,2:3,4-di-O-isopropylidene-α-D-galacto-hexodialdo-1,5-pyranose, methyl 2,3,4-tri-O-benzyl-D-hexodialdo-1,5-pyranosides with the gluco and manno configurations showed no preference for the formation of compounds with the D-glycero configuration. Attempts to achieve high diastereoselectivity in the conversion of L-glycero into the D-glycero isomers by oxidation at C-6 followed by reduction with L-selectride were unsuccessful with the thiazole adducts, but the desired products were formed in similar reactions of methyl 2,3,4-tri-O-benzyl-7-O-tert-butyldimethylsilyl-D-heptopyranosides. The approach to homologation in the altro series was thwarted by epimerization at C-5 in the attempted formation of methyl 2,3,4-tri-O-benzyl-α-D-altro-hexodialdo-1,5-pyranoside. The successful synthesis of methyl D-glycero-α-D-altro-heptopyranoside from methyl α-D-glucopyranoside was achieved by homologation followed by configurational alteration from the D-gluco to the D-altro series.

  对Campylobacter jejuni血清型O:23和O:36脂多糖O抗原链成分D-glycero-D-altro-heptose合成方法的探索，引导了对2-三甲基硅基噻唑同系化方法在庚糖合成中应用的研究。与从1,2:3,4-二-O-异亚丙基-α-D-半乳糖-己醛糖-1,5-吡喃糖形成1,2:3,4-二-O-异亚丙基-D-甘油-α-D-半乳糖-庚吡喃糖衍生物的差向异构选择性形成相比，具有葡萄糖和甘露糖构型的甲基2,3,4-三-O-苄基-D-己醛糖-1,5-吡喃糖苷在形成D-甘油构型化合物方面没有表现出偏好。尝试通过C-6氧化后用L-选择性还原剂将L-甘油转化为D-甘油异构体，在噻唑加合物中未能实现高差向异构选择性，但在甲基2,3,4-三-O-苄基-7-O-叔丁基二甲基硅基-D-庚吡喃糖苷的类似反应中形成了所需产物。在altro系列中进行同系化的方法因在尝试形成甲基2,3,4-三-O-苄基-α-D-altro-己醛糖-1,5-吡喃糖苷时C-5的差向异构化而受阻。从甲基α-D-葡萄糖苷成功合成了甲基D-甘油-α-D-altro-庚吡喃糖苷，通过同系化后从D-葡萄糖系列到D-altro系列构型改变实现。
• A versatile and new highly stereoselective approach to the synthesis of l-glycero-d-manno-heptopyranosides
  作者：G.J.P.H Boons、G.A van der Marel、J.H van Boom

  DOI：10.1016/s0040-4039(00)95167-0

  日期：1989.1

  The reaction of (phenyldimethyl)silylmethylmagnesium chloride with benzyl 2,3,4-tri-O-benzyl-α-D-manno-hexodialdo-1,5-pyranoside affords the corresponding L-glycero-D-manno-addition product having at C-7 the phenyldimethylsilyl (PDMSi) group. The latter silanyl compound survived benzylation as well as glycosylation at OH-6, and the PDMSi group could be unmasked with overall retention of configuration

  （苯基二甲基）甲硅烷基甲基镁氯化物与苄基2,3,4-三-O-苄基-α-D-甘露聚糖-己二醛-1,5-吡喃糖苷的反应得到相应的L-甘油-D-甘露聚糖-加成产物，其具有C-7为苯基二甲基甲硅烷基（PDMSi）。后者的甲硅烷基化合物在OH-6处的苄基化和糖基化作用下均能幸存下来，并且PDMSi基团可以被掩盖，从而保持整体构型，从而获得游离羟基。
• Studies of alkaline mediated phosphate migration in synthetic phosphoethanolamine l-glycero-d-manno-heptoside derivatives
  作者：Andrea Stewart、Christian Bernlind、Adele Martin、Stefan Oscarson、James C. Richards、Elke K.H. Schweda

  DOI：10.1016/s0008-6215(98)00271-7

  日期：1998.12

  subjected to strong alkaline conditions (4 M KOH, 120 °C, 18 h). The resulting products were analyzed by 1 H NMR spectroscopy and electrospray mass spectrometry. It was found that phosphate substituents were stable under these conditions and neither migration nor hydrolysis was observed except for the heptose 7-phosphate, which gave a substantial amount of phosphate hydrolysis. In phosphoethanolamine-substituted

  摘要甲基α-d-甘露吡喃糖苷的合成的2、3、4和6一磷酸酯衍生物，甲基l-甘油-α-d-甘露糖吡喃糖苷的4-，6-和7-单磷酸酯衍生物和相应的磷酸乙醇胺衍生物和甲基l-甘油-α-d-芒果基七吡喃糖苷的6,7-环磷酸酯类似物用于研究在强碱性条件下（4 M KOH，120°C，18 h）的磷酸盐迁移和水解。通过1 H NMR光谱和电喷雾质谱分析所得产物。发现在这些条件下磷酸酯取代基是稳定的，除了庚糖7-磷酸酯（其产生大量的磷酸酯水解）以外，未观察到迁移或水解。
• Synthesis of 2-(4-trifluoroacetamidophenyl)ethyl O-(spL-glycero-α-spD-manno-heptopyranosyl)-(1→7)-O-(spL-glycero-α-spD- manno-heptopyranosyl)-(1»3)-spL-glycero-α-spD-manno-heptopyranoside, coresponding to the heptose region of the Salmonella Ra core structure
  作者：Per J. Garegg、Stefan Oscarson、Helena Ritzén、Maria Szönyi

  DOI：10.1016/s0008-6215(00)90553-6

  日期：1992.4

  Abstract The title trisaccharide was synthesized from methyl 2,3,4-tri- O -benzyl- L - glycero -α- D - manno -heptopyranoside by acetolysis, followed by conversion into ethyl thioglycosides and also glycosyl bromides, which were borth used in glycoslyation reactions. In glycosylations using thioglycosides as glycosyl donors, N -iodosuccinimide-silver triflate and dimethyl(methylthio)sulfonium triflate

  摘要标题化合物由2,3,4-三-O-苄基-L-甘油-α-D-甘露聚糖-七吡喃糖苷经乙酰水解合成，然后转化为乙基硫代糖苷和糖基溴化物。糖基化反应。在使用硫代糖苷作为糖基供体的糖基化中，将N-碘代琥珀酰亚胺-三氟甲磺酸银和三氟甲磺酸二甲基（甲硫基）as用作促进剂，并且在与糖基溴化物的糖基化中使用三氟甲磺酸银。设计在标题三糖合成过程中引入中间体的保护基团，以允许在O-3'处进行稍后的糖基化反应，以产生沙门氏菌LPS核心区域的较大寡糖片段，并允许在O-4和0-4'，