methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-(methylene)-α-D-arabinohexopyranoside | 153082-00-9

• 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: methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-(methylene)-α-D-arabinohexopyranoside
• 英文别名: methyl 3,4,6-tri-O-benzyl-2-C-methylene-2-deoxy-α-D-arabino-hexopyranoside；methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-methylene-α-D-arabinohexopyranoside；methyl 3,4,6-tri-Obenzyl-2-deoxy-2-C-methylene-α-D-arabino-hexopyranoside；(2S,4R,5S,6R)-2-methoxy-3-methylidene-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• CAS: 153082-00-9
• 化学式: C₂₉H₃₂O₅
• 分子量: 460.57
• InChiKey: XQZZTFFZNZBOEN-OLQMUTRHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-(methylene)-α-D-arabinohexopyranoside 在 氢气 作用下， 以55%的产率得到methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-methyl-α-D-mannohexopyranoside
  参考文献：
  名称：

  New stable anomeric hydroperoxides derived from 2-deoxysugars; enantioselective epoxidation of 2-methyl-1,4-naphthoquinone

  摘要：

  3.5-Di- or 3,4,6-tri-O-substituted-2-deoxysugars or their glycosides can be oxidized with hydrogen peroxide in the presence of an acid catalyst to the corresponding anomeric hydroperoxides, which are relatively stable, can be separated into pure anomers by column chromatography and stored in a refrigerator without visible decomposition. The hydroperoxides thus obtained were used for the enantioselective epoxidation of 2-methyl-1,4-naphthoquinone with ees in the range 28-47%. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.04.009
• 作为产物：
  描述：

  (2R,3S,4R)-3,4-bis(benzyloxy)-2-((benzyloxy)methyl)-3,4-dihydro-2H-pyran-5-carbaldehyde 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 三氟化硼乙醚 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-(methylene)-α-D-arabinohexopyranoside
  参考文献：
  名称：

  A new ferrier system: 2-C-acetoxymethylglycals. A covenient entry to 2-C-methylene glycosides

  摘要：

  介绍了三-O-苄基-2-C-乙酰氧甲基苷的合成及随后的费里尔重排反应生成 2-C-亚甲基苷的过程。

  DOI：

  10.1039/c39930001394

文献信息

• Stereoselective synthesis of 2-C-methylene glycosides and disaccharides via direct allylic substitution of hydroxy group in benzylated glycals
  作者：Paramathevar Nagaraj、Namakkal G. Ramesh

  DOI：10.1016/j.tet.2009.11.082

  日期：2010.1

  InCl3 efficiently catalyzes allylic substitution of the hydroxy group of 2-C-hydroxymethyl glycals to afford a diversity of 2-C-methylene alkyl and aryl glycosides as well as disaccharides in high yields. This protocol surpasses the existing methods for the synthesis of 2-C-methylene glycosides as it obviates the need for functionalizing the allylic hydroxy group of glycals. The interest of this methodology

  InCl 3有效催化2- C-羟甲基糖基的羟基的烯丙基取代，以高收率提供各种2- C-亚甲基烷基和芳基糖苷以及二糖。该方案超越了用于合成2- C-亚甲基糖苷的现有方法，因为它消除了功能化糖基的烯丙基羟基的需要。该方法的兴趣在于，即使在糖基的烯丙基位置具有游离羟基，也仅需要催化量的InCl 3时，所需要的条件极为温和。该反应快速（30分钟），具有立体选择性，并且与各种含氧亲核试剂兼容，包括那些具有酸不稳定基团的亲核试剂。从2- C-羟甲基半乳糖直接形成α，α-（1→1）连接的二糖衍生物的机理研究表明，该反应通过多米诺重氮重排进行，然后进行容易的1，3-烷氧基迁移。
• Divergent synthesis of 2-C-branched pyranosides and oxepines from 1,2-gem-dibromocyclopropyl carbohydrates
  作者：Peter W. Moore、Julia K. Schuster、Russell J. Hewitt、M. Rhia L. Stone、Paul H. Teesdale-Spittle、Joanne E. Harvey

  DOI：10.1016/j.tet.2014.06.069

  日期：2014.9

  The ring opening of 1,2-(gem-dibromo)cyclopropyl carbohydrates by two different modes leads to either 2-C-(bromomethylene)pyranosides (using base) or 2-bromooxepines (using silver salts), as shown previously by us for a d-glucal-derived cyclopropane. The base-promoted ring opening is extended to encompass additional alcohol, thiol and amine nucleophiles, and diastereoisomeric cyclopropane precursors

  开环的1,2-（宝石二溴）环丙基碳水化合物由两种不同的模式导致要么2- Ç - （溴亚甲基）吡喃糖苷（使用碱）或2- bromooxepines（使用银盐），如我们之前显示一d -glucal衍生环丙烷。碱促进的开环扩展到涵盖其他醇，硫醇和胺亲核试剂以及非对映异构体环丙烷前体。2- C-（溴亚甲基）吡喃糖苷的交叉偶联导致扩展的2- C-支化吡喃糖苷。描述了在各种醇的存在下银促进的环丙基碳水化合物的环扩环。生成的苄基2-溴氧杂环丁烷的交叉偶联得到2- C取代的奥沙平。
• InCl₃-Catalyzed Rapid 1,3-Alkoxy Migration in Glycal Ethers: Stereoselective Synthesis of Unsaturated α-<i>O</i>-Glycosides and an α,α-(1→1)-Linked Disaccharide
  作者：Paramathevar Nagaraj、Namakkal G. Ramesh

  DOI：10.1002/ejoc.200800453

  日期：2008.9

  facile stereoselective 1,3-migration of allylic ethers of glycals to afford 2-C-methylene- and 2,3-unsaturated-α-O-glycosides in high yields. The reaction is rapid (10 min), requires only 20 mol-% of the catalyst, and is compatible with acid-labile functional groups such as epoxides and acetals. This methodology provides a convenient alternative to the Ferrier rearrangement. A direct synthesis of an

  InCl3 催化乙二醇烯丙醚的简单立体选择性 1,3-迁移，以高产率提供 2-C-亚甲基-和 2,3-不饱和-α-O-糖苷。反应迅速（10 分钟），仅需要 20 mol% 的催化剂，并且与酸不稳定的官能团（如环氧化物和缩醛）相容。这种方法为 Ferrier 重排提供了一种方便的替代方法。还报道了通过多米诺法直接合成 α,α-(11)-连接的二糖衍生物。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）
• Synthesis of C-2 methylene glycosides from C-2 propargyloxymethyl glycals exploiting the alkynophilicity of AuCl3
  作者：Sudhir Kashyap、Srinivasa Rao Vidadala、Srinivas Hotha

  DOI：10.1016/j.tetlet.2007.10.144

  日期：2007.12

  C-2 Methylene glycosides were synthesized from C-2 propargyloxymethyl glycals in a stereoselective manner using a catalytic quantity of AuCl3. The Au-catalyzed reaction was explored using various aglycones. The current protocol enables the preparation of C-2 methylene glycosides, tolerates diverse functional groups and is fast, catalytic and mild. (c) 2007 Elsevier Ltd. All rights reserved.
• Synthesis of Oxepines and 2-Branched Pyranosides from a <scp>d</scp>-Glucal-Derived <i>gem</i>-Dibromo-1,2-cyclopropanated Sugar
  作者：Russell J. Hewitt、Joanne E. Harvey

  DOI：10.1021/jo902306a

  日期：2010.2.5

  The conversion of cyclopropane-fused carbohydrates into oxepines is an attractive method for accessing diverse members of the septanoside family of carbohydrate mimetics. 2-Bromooxepines are obtained through silver(I)-promoted thermal ring expansion of a D-glucal-derived gem-dihalocyclopropanated sugar. In contrast, cyclopropane ring cleavage under basic conditions leads to 2-C-branched pyranosides, not the 2-bromooxepine structures assigned in an earlier report.