1,2-C-(dichloromethylene)-α-D-glycerohexitol | 1094382-79-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2-C-(dichloromethylene)-α-D-glycerohexitol
• 英文别名: (1S,3R,4R,5S,6S)-4,5,6-tri(benzyloxy)-3-((benzyloxy)methyl)-7,7-dichloro-2-oxabicyclo[4.1.0]heptane；1,5-anhydro-2,3,4,6-tetra-O-benzyl-1,2-C-(dichloromethylene)-α-D-glycero-D-galacto-hexitol；(1S,3R,4R,5S,6S)-7,7-dichloro-4,5,6-tris(phenylmethoxy)-3-(phenylmethoxymethyl)-2-oxabicyclo[4.1.0]heptane
• CAS: 1094382-79-2
• 化学式: C₃₅H₃₄Cl₂O₅
• 分子量: 605.558
• InChiKey: PKIMMRJOPVOKEG-ZOHVZMGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  42
• 可旋转键数：
  13
• 环数：
  6.0
• 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：

  1,2-C-(dichloromethylene)-α-D-glycerohexitol 在 18-冠醚-6 、 苄基三乙基氯化铵 、 potassium carbonate 、 sodium hydroxide 作用下， 以 氯仿 、 甲苯 为溶剂， 反应 80.0h， 生成 2,3,4-tri-O-benzyl-6-O-(2-chloro-2-deoxy-3,4,5,7-tetra-O-benzyl-α-D-arabino-hept-2-eno-septanosyl)-1,5-anhydro-1,2-C-(dichloromethylene)-α-D-glycero-D-galacto-hexitol
  参考文献：
  名称：

  葡糖苷中糖苷键的水解：单-，二-和2-氯-2-脱氧-庚糖苷的比较。

  摘要：

  本文报道了在酸催化下一氯，二氯和2-氯-2-脱氧Septanosides的水解稳定性的动力学研究。单糖苷和二糖苷的比较表明，二糖中的糖苷键比单糖更稳定。此外，还原端的糖苷键水解几乎是二糖非还原端的糖苷键水解速度的两倍。发现2-氯-2-脱氧庚糖苷是最稳定的，并且其糖苷键水解仅在升高的温度下发生。建议外环羟甲基的取向和诱导作用在水解速率中起作用。

  DOI：

  10.1016/j.carres.2014.05.013
• 作为产物：
  描述：

  2,3,4,6-tetra-O-benzyl 1,5-anhydro-D-arabino-hex-1-enitol 、 氯仿 在 苄基三乙基氯化铵 、 sodium hydroxide 作用下， 以 水 为溶剂， 反应 6.0h， 以81%的产率得到1,2-C-(dichloromethylene)-α-D-glycerohexitol
  参考文献：
  名称：

  葡糖苷中糖苷键的水解：单-，二-和2-氯-2-脱氧-庚糖苷的比较。

  摘要：

  本文报道了在酸催化下一氯，二氯和2-氯-2-脱氧Septanosides的水解稳定性的动力学研究。单糖苷和二糖苷的比较表明，二糖中的糖苷键比单糖更稳定。此外，还原端的糖苷键水解几乎是二糖非还原端的糖苷键水解速度的两倍。发现2-氯-2-脱氧庚糖苷是最稳定的，并且其糖苷键水解仅在升高的温度下发生。建议外环羟甲基的取向和诱导作用在水解速率中起作用。

  DOI：

  10.1016/j.carres.2014.05.013

文献信息

• Synthesis of Aryl, Glycosyl, and Azido Septanosides through Ring Expansion of 1,2-Cyclopropanated Sugars
  作者：N. Vijaya Ganesh、N. Jayaraman

  DOI：10.1021/jo801967s

  日期：2009.1.16

  septanosides, arabinofuranosyl and glucopyranosyl septanoside disaccharides, and azido septanosides is reported. A cyclopropanated adduct of the oxyglycal upon reaction with phenols, sugars, and azide led to the formation of ring-expanded septanoside derivatives. The ring expansion was found to be stereoselective with sugars, whereas phenols and the azide afforded an anomeric mixture of the ring expanded

  报道了一种用于制备芳基Septanosides，阿拉伯呋喃糖基和吡喃葡萄糖基Septanoside二糖和叠氮基Septanosides的扩环方法。与苯酚，糖和叠氮化物反应后，氧丙二醇的环丙烷化加合物导致形成环膨胀的番石榴糖苷衍生物。发现扩环对糖是立体选择性的，而酚和叠氮化物提供了扩环产物的异头混合物。进一步观察到，使用NaBH 4将中间二酮转化为二醇，对于隔酒苷的α-端异构体具有很高的非对映选择性。该报告进一步巩固了氧糖环扩环方法的通用性，以制备在其还原端具有不同取代基的Septanosides。
• Exclusive ring opening of gem-dihalo-1,2-cyclopropanated oxyglycal to oxepines in AgOAc
  作者：Supriya Dey、N. Jayaraman

  DOI：10.1016/j.carres.2014.01.023

  日期：2014.5

  Treatment of gem-dihalo-1,2-cyclopropanated D-oxyglycal with primary, secondary, and unsaturated alcohols, in the presence of AgOAc, leads to the formation of chloro-oxepines exclusively. Reaction of the resulting 2-chloro-oxepines with excess alcohol in the presence of AgOAc, do not promote further reactions. This result is in contrast to the reactions of D-glucal derived halo-oxepine with alcohols known previously that lead to the formation of furanoses as the major product under similar reaction conditions. Observation of this study consolidates the reactivity differences of gem-dihalo-1,2-cyclopropanated oxyglycals, as compared to gem-dihalo- 1,2-cyclopropanated glycals. (C) 2014 Elsevier Ltd. All rights reserved.
• Dense network of OH⋯O and CH⋯O interactions in the solid state structure of n-pentyl-2-chloro-2-deoxy-α-d-manno-sept 3-uloside
  作者：Supriya Dey、Krishnayan Basuroy、N. Jayaraman

  DOI：10.1016/j.carres.2014.04.019

  日期：2014.7

  Single crystal X-ray structural analysis of a septanoside, namely, n-pentyl-2-chloro-2-deoxy sept-3-uloside (1) provides many finer details of the molecular structure, in addition to its preferred twist-chair conformation, namely, (TC3,4)-T-5,6 conformation. Structural analysis reveals a dense network of O-H...O, C-H...O and van der Waals interactions that stabilize interdigitized, planar bi-layer structure of the crystal lattice. (C) 2014 Elsevier Ltd. All rights reserved.
• Solid state structure of p-bromo phenyl 4,5,7-tri-O-benzyl-β-d-glycero-d-talo-septanoside and an analysis of non-covalent interactions
  作者：Supriya Dey、Krishnayan Basuroy、N. Jayaraman

  DOI：10.1016/j.carres.2015.03.020

  日期：2015.6

  The solid state structure of a new seven-membered sugar oxepane derivative, namely, p-bromo phenyl 4,5,7-tri-O-benzyl-beta-D-glycero-D-talo-septanoside is discussed, as determined through single crystal X-ray structural determination and in relation to their conformational features. The molecule adopts twist-chair as the preferred conformation, with conformational descriptor (TC2,3)-T-0,1. The solid state packing of molecules is governed by a rich network of non-covalent bonding originating from O-H center dot center dot center dot O, C-H center dot center dot center dot pi, C-H center dot center dot center dot Br and aromatic pi center dot center dot center dot pi interactions that stabilize the packing of molecules in the crystal. (C) 2015 Elsevier Ltd. All rights reserved.
• Glycosidic bond hydrolysis in septanosides: a comparison of mono-, di-, and 2-chloro-2-deoxy-septanosides
  作者：Supriya Dey、N. Jayaraman

  DOI：10.1016/j.carres.2014.05.013

  日期：2014.11

  A kinetic study of the hydrolytic stabilities of mono-, di-, and 2-chloro-2-deoxy septanosides, under acid-catalysis, is reported herein. A comparison of mono- and diseptanosides, shows that the glycosidic bond in the disaccharide is more stable than the monosaccharide. Further the glycosidic bond at the reducing end hydrolyzes almost twice as faster than that of the non-reducing end of the disaccharide

  本文报道了在酸催化下一氯，二氯和2-氯-2-脱氧Septanosides的水解稳定性的动力学研究。单糖苷和二糖苷的比较表明，二糖中的糖苷键比单糖更稳定。此外，还原端的糖苷键水解几乎是二糖非还原端的糖苷键水解速度的两倍。发现2-氯-2-脱氧庚糖苷是最稳定的，并且其糖苷键水解仅在升高的温度下发生。建议外环羟甲基的取向和诱导作用在水解速率中起作用。