3,4,6-tri-O-benzyl-1,5-anhydro-2-deoxy-1,2-C-methylene-D-glycero-D-gulohexitol | 162428-31-1

• 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: 3,4,6-tri-O-benzyl-1,5-anhydro-2-deoxy-1,2-C-methylene-D-glycero-D-gulohexitol
• 英文别名: (1R,3R,4S,5R,6S)-4,5-bis(phenylmethoxy)-3-(phenylmethoxymethyl)-2-oxabicyclo[4.1.0]heptane
• CAS: 162428-31-1
• 化学式: C₂₈H₃₀O₄
• 分子量: 430.544
• InChiKey: KNARNYHTGSHJAX-DJOAIXOZSA-N

物化性质

• 沸点：
  558.7±50.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-1,5-anhydro-2-deoxy-1,2-C-methylene-D-glycero-D-gulohexitol 在 N-溴代丁二酰亚胺(NBS) 、 水 作用下， 以 1,4-二氧六环 为溶剂， 反应 8.0h， 以66%的产率得到(3R,4R,5S,6R)-4,5-Bis-benzyloxy-6-benzyloxymethyl-3-bromomethyl-tetrahydro-pyran-2-ol
  参考文献：
  名称：

  Synthesis and Reactions of 1,2-Cyclopropanated Sugars

  摘要：

  Diastereospecific cyclopropanation of glycals 1, 2, 3, 4, and 41 was carried out using either dihalocarbene addition or zinc-carbenoid addition to yield 1,2-cyclopropanated sugars. Dichloro- and dibromocarbenes added stereoselectively anti to the C-3 benzyloxy group, whereas (under Simmons-Smith conditions) the cyclopropanes were formed syn to the same substituent. The reactions of these 1,2-cyclopropanated sugars to provide either ring expanded glycosides or C-2-branched chain glycosides were explored. Solvolytic ring expansion of 1,2-dibromocyclopropanated sugars with K2CO3 in refluxing methanol yielded the corresponding chiral oxepins 20-22. Electrophilic ring openings of parent cyclopropanes (14 and 17 derived from glucal 1) were carried out with different electrophiles to give functionalized 2-deoxy-2-C-branched chain glycosides. The ring openings of 14 in different solvents resulted in both alpha- and beta-anomers, whereas 17 gave exclusively the alpha-anomer.

  DOI：

  10.1021/jo970948k
• 作为产物：
  描述：

  (3R,4R,5S)-4,5-Bis-benzyloxy-3-benzyloxymethyl-2,7-dioxa-bicyclo[4.1.0]heptane 在 sodium hydroxide 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 3,4,6-tri-O-benzyl-1,5-anhydro-2-deoxy-1,2-C-methylene-D-glycero-D-gulohexitol
  参考文献：
  名称：

  Cytotoxic effects of C-glycosides in HOS and HeLa cell lines

  摘要：

  Fifty-two C-glycosides were synthesized and their in-vitro antiproliferative activity screened against human cervical carcinoma (HeLa) and osteosarcoma (HOS) cell lines. Nine of them had growth inhibitions (GI(50) values) below 10 mu M, the Gglucopyranoside 38 being the most active against HeLa (5.4 mu M) and the dichlorocyclopropyl derivative 42 against HOS (1.6 mu M). Some preliminary structure-activity relationships were established. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2007.04.060

文献信息

• Platinum-Catalyzed Ring Opening of 1,2-Cyclopropanated Sugars with <i>O</i>-Nucleophiles. Convenient Synthesis of 2-<i>C</i>-Branched Carbohydrates
  作者：Jürgen Beyer、Philip R. Skaanderup、Robert Madsen

  DOI：10.1021/ja001558+

  日期：2000.10.1

  in the ring opening with alcohols regardless of the stereochemistry of the starting cyclopropane. When electron-rich phenols are employed as O-nucleophiles, rearrangement to the glycosyl arene has been observed. In general, the ring opening occurs readily with unsubstituted sugar cyclopropanes to give 2-C-methyl carbohydrates. However, cyclopropanes with ester or alkyl substituents are significantly

  描述了一种由 Zeise 的二聚体催化的新反应，该反应允许 1,2-环丙烷化糖与 O-亲核试剂开环，得到 2-C-支链碳水化合物。许多 O-亲核试剂可以参与开环，包括醇类、酚类和水。已使用范围广泛的醇，产生从简单的甲基糖苷到更复杂的二糖的 2-C 支链糖苷。在新形成的 C-1 立体中心获得了非常高的非对映选择性。无论起始环丙烷的立体化学如何，α-糖苷受异头效应的青睐，始终是与醇开环的主要产物。当富电子酚用作 O-亲核试剂时，已观察到重排为糖基芳烃。一般来说，未取代的糖环丙烷很容易开环，得到 2-C-甲基碳水化合物。然而，带有酯或烷基取代基的环丙烷反应性明显较低，有些甚至完全在...
• A New Procedure for Highly Regio‐ and Stereoselective Iodoacetoxylation of Protected Glycals and α‐1,2‐Cyclopropanated Sugars
  作者：David W. Gammon、Henok H. Kinfe、Dirk E. De Vos、Pierre A. Jacobs、Bert F. Sels

  DOI：10.1080/07328300701351524

  日期：2007.5.31

  less than 2 h at low temperatures to 2‐deoxy‐2‐iodoglycosyl acetates or novel 2‐deoxy‐2‐iodomethylglycosyl acetates using the simple, inexpensive reagent mixture of ammonium iodide, hydrogen peroxide, and acetic anhydride/acetic acid in acetonitrile. The protected glycals gave rise to 2‐deoxy‐2‐bromoglycosyl acetates when ammonium bromide was used instead of the iodide, although longer reaction times

  使用简单，廉价的方法，在低温下不到2小时的时间内，可以在不到2小时的时间内以高收率和高选择性将受保护的糖和α-1,2-环丙烷化的糖转化为2-脱氧-2-碘代糖基乙酸酯或新型2-脱氧-2-碘甲基糖基乙酸酯。碘化铵，过氧化氢和乙酸酐/乙酸在乙腈中的试剂混合物。当使用溴化铵代替碘化物时，尽管需要更长的反应时间并且选择性较差，但受保护的糖类会生成2-脱氧-2-溴代糖基乙酸酯。其他简单的烯烃，例如苯乙烯和茚，也被转化为它们相应的1,2-反-碘乙酸酯。
• Synthesis of 1,2-cyclopropanated sugars from glycals
  作者：R. Murali、C. V. Ramana、M. Nagarajan

  DOI：10.1039/c39950000217

  日期：——

  Syntheses of both forms of cyclopropanated sugars from glycals by (i) Simmons–Smith reaction and (ii) dichiorocarbene addition followed by dehalogenation are described.

  描述了通过(i) Simmons–Smith反应和(ii) 二氯甲烯添加后去卤化的方法合成两种形式的环丙烷糖。
• Studies Towards the Synthesis of the C29-C51 Fragment of Altohyrtin A
  作者：Eduardo Fernandez-Megia、Nelly Gourlaouen、Steven V. Ley、Gareth J. Rowlands

  DOI：10.1055/s-1998-3140

  日期：1998.9

  The synthesis of the highly substituted E and F pyran fragment 23 of altohyrtin A 1 from tri-O-benzyl-d-glucal 5 is described. The synthesis of a model compound 31 containing the altohyrtin A triene side-chain outlines the proposed strategy for the elaboration of the F pyran.

  本文介绍了从三-O-苄基-d-葡萄糖醛 5 中合成高度取代的阿尔托黄素 A 1 的 E 和 F 吡喃片段 23 的过程。含有阿托菌素 A 三烯侧链的模型化合物 31 的合成概述了拟议的 F 吡喃化合物的合成策略。
• A Facile Synthesis of Chiral α-Methylene-δ-Valerolactones
  作者：C. Ramana、M. Nagarajan

  DOI：10.1055/s-1997-5764

  日期：1997.7

  Chiral α-methylene-δ-valerolactones have been obtained from 1,2-cyclopropanated sugars in one pot by reaction with iodonium di(s-collidine)perchlorate (IDCP).

  手性α-亚甲基-β-戊内酯是通过一锅中的 1,2-环丙烷糖与二(s-可力丁)高氯酸碘 (IDCP) 反应获得的。