methyl α-D-xylopyranoside 4-benzyl ether | 69984-20-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl α-D-xylopyranoside 4-benzyl ether
• 英文别名: methyl 4-O-benzyl-β-D-xylospyranoside；methyl 4-O-benzyl-β-D-xylopyranoside；Methyl-4-O-benzyl-β-D-xylopyranosid；(2R,3R,4R,5R)-2-methoxy-5-phenylmethoxyoxane-3,4-diol
• CAS: 69984-20-9
• 化学式: C₁₃H₁₈O₅
• 分子量: 254.283
• InChiKey: LBIITPLCZVCVQD-YVECIDJPSA-N

物化性质

• 沸点：
  406.4±45.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl α-D-xylopyranoside 4-benzyl ether 在 palladium on activated charcoal 氢溴酸 、 氢气 、 氰化汞 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 生成 O-(2,3-di-O-acetyl-4-O-benzyl-β-D-xylopyranosyl)-(1->4)-O-(2,3-di-O-acetyl-β-D-xylopyranosyl)-(1->4)-1,2,3-tri-O-acetyl-β-D-xylopyranose
  参考文献：
  名称：

  Systematic, sequential synthesis of (1→4)-β-d-xylo-ligosaccharides and their methyl β-glycosides

  摘要：

  DOI：

  10.1016/s0008-6215(00)85935-2
• 作为产物：
  描述：

  methyl 2,3-O-isopropylidene-β-D-xylopyranoside 在 甲醇 、 氢氧化钾 、 H+ resin 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成 methyl α-D-xylopyranoside 4-benzyl ether
  参考文献：
  名称：

  Regioselective protection strategies for D-xylopyranosides

  摘要：

  The acylation of D-xylopyranosides can be effected at any position by selective hydroxyl activation with dibutyltin oxide in refluxing benzene and proper choice of starting anomer. Methyl 4-O-benzyl-beta-D-xylopyranoside, available from methyl 2,3-O-isopropylidene-beta-D-xylopyranoside, provides the 2- and 3-benzoates, which are easily separable in 85% combined yield. Methyl and allyl beta-D-xylopyranosides, when treated with 1 equiv of dibutyltin and subsequently with benzoyl chloride (1 equiv), yield their corresponding 4-benzoates (80%). The use of 2 equiv of benzoyl chloride provides the 3,4-dibenzoates in excellent yield (90%). The clean conversion to mono- or dibenzoates, depending on the amount of benzoyl chloride added, suggests that the intermediate stannylene acetals provide different activation levels. A pathway involving acylation of an intermediate dibutylchlorostannyl ether is proposed to explain the observed phenomenon. This sequential selective activation is used to afford protection and differentiation of the 3- and 4-positions with a one-pot synthesis of methyl 4-O-benzoyl-3-O-(chloroacetyl)-beta-D-xylopyranoside. Methyl and benzyl alpha-D-xylopyranosides afford the 2,4-dibenzoates in good yield (> 80%) demonstrating 1,3-activation of a triol system. This protection strategy is used to prepare benzyl O-(2,3,5-tri-O-benzoyl-alpha-L-arabinofuranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-D-xylopyranoside from D-xylose and L-arabinose. In the final step, the silver triflate catalyzed glycosylation of benzyl 2,4-di-O-benzoyl-alpha-D-xylopyranoside by 2,3,5-tri-O-benzoyl-alpha-L-arabinofuranosyl chloride is accomplished in 91% yield.

  DOI：

  10.1021/jo00025a013

文献信息

• Tin-Mediated Regioselective Benzylation and Allylation of Polyols: Applicability of a Catalytic Approach Under Solvent-Free Conditions
  作者：Maddalena Giordano、Alfonso Iadonisi

  DOI：10.1021/jo402399n

  日期：2014.1.3

  The first catalytic version of the stannylene-mediated benzylation and allylation of polyols is reported. The methodology is based on a simple solvent-free protocol that significantly advances, in terms of both experimental ease and synthetic scope, the applicability of tin-promoted selective protections. The described approach is indeed endowed with a very large number of advantages over routine protocols:

  报道了由亚苯乙烯介导的多元醇的苄基化和烯丙基化的第一个催化形式。该方法基于简单的无溶剂方案，在实验简便性和合成范围方面，都大大提高了锡促进的选择性保护的适用性。与常规方案相比，所描述的方法确实具有许多优点：使用低催化负载量的廉价Bu 2SnO是避免使用溶剂的一步法工艺，是在空气中进行反应的最低要求的实验程序，缩短了反应时间，简化了后处理工艺，目标范围广，在许多情况下，收率均优于常规协议。另外，无催化溶剂的方法将亚锡烷基化学的范围扩展到了空前的应用领域，以还原糖和合成高苄基化的结构单元，而这些过程可以通过更苛刻的程序来获得。从概念的角度来看，所描述的结果表明，无溶剂条件可以帮助开发催化方法，否则该方法在溶液中无效。
• Deoxy and deoxyfluoro analogues of acetylated methyl β-d-xylopyranoside––substrates for acetylxylan esterases
  作者：Mária Mastihubová、Peter Biely

  DOI：10.1016/j.carres.2004.06.001

  日期：2004.8

  synthesized via 2,3-anhydropentopyranoside precursors. Methyl 2,3-anhydro-4-O-benzyl-beta-D-ribopyranoside was transformed into methyl 2,3-anhydro-4-O-benzyl-beta-D-lyxopyranoside in three steps. The epoxide ring opening of 2,3-anhydropentopyranosides was accomplished either by hydride reduction or hydrofluorination. Methyl beta-D-xylopyranoside 2,3,4-tri-O-, 2,4-di-O-, and 3,4-di-O-acetates, and the prepared

  通过2,3合成了乙酰氧基木聚糖酯酶，二-O-乙酰化甲基β-D-吡喃吡喃糖苷的2-脱氧，3-脱氧，2-脱氧-2-氟和3-脱氧-3-氟衍生物的四种修饰底物-脱水戊吡喃糖苷前体。通过三个步骤将甲基2,3-脱水-4-O-苄基-β-D-核吡喃糖苷转化为甲基2,3-脱水-4-O-苄基-β-D-核吡喃糖苷。通过氢化物还原或氢氟化来完成2，3-脱水戊基吡喃糖苷的环氧开环。测试了β-D-吡喃吡喃二甲基2,3,4-tri-O-，2,4-di-O-和3,4-di-O-乙酸酯和制备的二乙酸酯类似物作为乙酰木聚糖酯酶底物的来源裂褶菌公社和里氏木霉。其脱乙酰基速率的测量指出了底物酶的独特结构要求。
• Haque, Mohammed Ekramul; Kikuchi, Tohru; Yoshimoto, Kimihiro, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 6, p. 2243 - 2255
  作者：Haque, Mohammed Ekramul、Kikuchi, Tohru、Yoshimoto, Kimihiro、Tsuda, Yoshisuke

  DOI：——

  日期：——
• Schraml, Jan; Petrakova, Eva; Pihar, Otomar, Collection of Czechoslovak Chemical Communications, 1983, vol. 48, # 7, p. 1829 - 1841
  作者：Schraml, Jan、Petrakova, Eva、Pihar, Otomar、Hirsch, Jan、Chvalovsky, Vaclav

  DOI：——

  日期：——
• Glycosylation of methyl-2,3-di-O-acetyl-?-D-xylopyranoside triarylmethyl ethers with electron-donor substituents in the aromatic ring by 3,4-di-O-acetyl-1,2-O-[1-(endo-cyano)-ethylidene]-?-D-xylo-pyranose
  作者：N. E. Nifant'ev、L. V. Bakinovskii、Yu. E. Tsvetkov、N. K. Kochetkov

  DOI：10.1007/bf00962335

  日期：1987.4