methyl 2,3-di-O-benzyl-4-O-(2-naphthyl)methyl-α-D-glucopyranoside | 291314-27-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3-di-O-benzyl-4-O-(2-naphthyl)methyl-α-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-6-methoxy-3-(naphthalen-2-ylmethoxy)-4,5-bis(phenylmethoxy)oxan-2-yl]methanol
• CAS: 291314-27-7
• 化学式: C₃₂H₃₄O₆
• 分子量: 514.618
• InChiKey: MARUSZSQYNWCPM-VJLURNNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-benzyl-4-O-(2-naphthyl)methyl-α-D-glucopyranoside 在 吡啶 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 methyl 2,3-di-O-benzyl-6-deoxy-6-C-(ethyl sulfonatomethyl)-4-O-(2'-naphthyl)methyl-α-D-glucopyranoside
  参考文献：
  名称：

  通过亲核取代合成 6-磺基甲基硫糖苷：防止硫糖苷 6-O-三氟甲磺酸酯 1→6 异头基团迁移的方法

  摘要：

  描述了通过相应 6-O-三氟甲磺酸酯的亲核置换将磺基甲基部分引入硫糖苷的主要位置。通过使用 α-硫糖苷或构象锁定的 β-硫糖苷作为起始材料，可以防止异头基团从构象灵活的 β-硫糖苷中不可避免地通过双环锍离子中间体发生 1→6 迁移。硫糖苷 6-磺酸在合成含肝素三糖的糖醛酸过程中表现出优异的 α 选择性。

  DOI：

  10.1002/ejoc.201300681
• 作为产物：
  描述：

  methyl 2,3-di-O-benzyl-4,6-O-(2-naphthyl)methylene-α-D-glucopyranoside 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 methyl 2,3-di-O-benzyl-4-O-(2-naphthyl)methyl-α-D-glucopyranoside
  参考文献：
  名称：

  糖苷的（2-萘基）亚甲基缩醛的制备及其氢解转化为2-萘基甲基（NAP）醚†

  摘要：

  糖苷的二恶烷和二恶烷型（2-萘基）亚甲基缩醛是通过酸催化的反缩醛化反应制备的。使用AlH 3（LiAlH 4：AlCl 3 = 3：1），NaCNBH 3 -HCl或BH 3 Me 3 N-AlCl 3试剂裂解乙缩醛。4，6- O-乙缩醛与AlH 3的反应产生了4- O NAP醚，而其他两种试剂则得到了具有优异区域选择性的6- O NAP衍生物。在二氧戊环型缩醛中，所有三种试剂的裂解方向由缩醛中心的立体化学确定。赤道ø NAP /轴向羟基衍生物是从所获得的外萘基异构体; 另一方面，内萘基乙缩醛引起轴向O NAP /赤道羟基化合物的形成。NAP醚和（2-萘基）亚甲基缩醛保护基都可以通过用DDQ处理而容易地除去。

  DOI：

  10.1016/s0040-4039(00)00735-8

文献信息

• Toward Synthesis of the Isosteric Sulfonate Analogues of the AT-III Binding Domain of Heparin
  作者：Mihály Herczeg、László Lázár、Anikó Borbás、András Lipták、Sándor Antus

  DOI：10.1021/ol900952d

  日期：2009.6.18

  d-Glucuronate and l-iduronate containing disaccharides related to the antithrombin-binding pentasaccharide of heparin, in which one of the sulfate esters is systematically replaced by a sodium sulfonatomethyl moiety, were synthesized. The sulfonic acid group was introduced by stereoselective radical addition onto the exomethylene moiety of the appropriate glycoside derivatives, and the resulting sulfonatomethyl

  合成了含有与肝素的抗凝血酶结合的五糖有关的二糖的d-葡萄糖醛酸酯和1-异丁酸酯，其中硫酸酯之一被磺基磺酸钠部分系统地取代。通过立体选择性自由基加成将磺酸基团引入适当糖苷衍生物的外亚甲基部分上，并将所得的磺酰基甲基葡糖苷用作受体。
• Deuterium-isotope study on the reductive ring opening of benzylidene acetals
  作者：I-Chi Lee、Medel Manuel L. Zulueta、Chi-Rung Shie、Susan D. Arco、Shang-Cheng Hung

  DOI：10.1039/c1ob06056b

  日期：——

  were prepared to probe the stereoselectivity of the reductive ring opening of carbohydrate-based benzylidene-type acetals. AlD3 revealed a retentive stereoselectivity probably through the rare SNi (internal nucleophilic substitution) mechanism. An SN1-like mechanism occurs in the acid-promoted regioselective BD3·THF- or Et3SiD-reductive ring opening.

  制备了特定的氘代参比化合物以探测基于碳水化合物的亚苄基型乙缩醛的还原性开环的立体选择性。AlD 3可能通过罕见的S N i（内部亲核取代）机制显示出保持性立体选择性。在酸促进的区域选择性BD 3 ·THF-或Et 3 SiD-还原性开环中发生类似S N 1的机制。
• Sequential removal of the benzyl-type protecting groups PMB and NAP by oxidative cleavage using CAN and DDQ
  作者：Joseph A Wright、Jinquan Yu、Jonathan B Spencer

  DOI：10.1016/s0040-4039(01)00563-9

  日期：2001.6

  The selective cleavage of the PMB (4-methoxybenzyl) group in the presence of the NAP (2-naphthylmethyl) group was achieved using CAN with a range of mono-saccharides. The NAP group can then be removed selectively in the presence of a benzyl group using DDQ. This provides a strategy for sequential deprotection of hydroxyl groups. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Large-scale synthesis of 6-deoxy-6-sulfonatomethyl glycosides and their application for novel synthesis of a heparinoid pentasaccharide trisulfonic acid of anticoagulant activity
  作者：Erika Mező、Mihály Herczeg、Dániel Eszenyi、Anikó Borbás

  DOI：10.1016/j.carres.2014.02.012

  日期：2014.3

  Multigram-scale syntheses of three 6-deoxy-6-sulfonatomethyl a-glucosides were accomplished via reactions of the corresponding primary triflate derivatives with the lithiated ethyl methanesulfonate. Chemoselective glycosylation reactions of different 6-C-sulfonatomethyl glucoside donors were studied. The sulfonic acid-containing building blocks were utilised in a novel [2+3] block synthesis of a trisulfonic acid isoster of the anticoagulant pentasaccharide idraparinux. (C) 2014 Elsevier Ltd. All rights reserved.
• Dioxane-type (2-naphthyl)methylene acetals of glycosides and their hydrogenolytic transformation into 6-O- and 4-O-(2-naphthyl)methyl (NAP) ethers
  作者：Anikó Borbás、Zoltán B Szabó、László Szilágyi、Attila Bényei、András Lipták

  DOI：10.1016/s0040-4020(02)00515-x

  日期：2002.7

  alpha-, beta-D-Gluco-, galacto-, 2-deoxy-2-phthalimido-beta-D-glucopyranosides with different aglycons (methyl, allyl, p-methoxyphenyl, thioethyl) reacted with 2-naphthaldehyde dimethyl acetal to give rise to 4,6-O-(2-naphthyl)methylene acetals. The acetals were converted into fully protected compounds bearing benzoyl, benzyl, allyl, p-methoxybenzyl groups. The fully alkylated dioxane-type acetals were hydrogenolysed with AlH3 (3LiAlH(4)-AlCl3) reagent to furnish 4-O-NAP/6-OH derivatives. All acetals were treated with BH3.Me3N-AlCl3 in THF and a reverse regioselectivity was observed, producing 6-O-NAP/4-OH derivatives. Similar regioselectivity was also observed by using NaCNBH3-HCl reagent. In all reactions very mild reaction conditions were required, regioselectivity was better than 93:7, and the isolated yields were between 83-92%. All compounds were characterised by H-1 and C-13 NMR spectra. Solid-state and solution conformation of methyl 2,3-di-O-acetyl-4,6-O-(2-naphthyl)methylene-a-D-galactopyranoside were elucidated by X-ray and NMR measurements. (C) 2002 Elsevier Science Ltd. All rights reserved.