methyl 2-O-benzyl-6,7-dideoxy-3,4-O-isopropylidene-β-D-galacto-hept-6-enopyranoside | 207346-81-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: methyl 2-O-benzyl-6,7-dideoxy-3,4-O-isopropylidene-β-D-galacto-hept-6-enopyranoside
• 英文别名: (3aS,4R,6R,7R,7aS)-4-ethenyl-6-methoxy-2,2-dimethyl-7-phenylmethoxy-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran
• CAS: 207346-81-4
• 化学式: C₁₈H₂₄O₅
• 分子量: 320.386
• InChiKey: OLYGTRYGEUXDFI-DRRXZNNHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 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 2-O-benzyl-6,7-dideoxy-3,4-O-isopropylidene-β-D-galacto-hept-6-enopyranoside 在 四(三苯基膦)钯 、 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 生成 (1S,2S,3S,4S,5R)-2-O-benzyl-5-ethenyl-3,4-O-isopropylidenecyclopentanetetraol 、 (1R,2S,3S,4S,5S)-2-O-benzyl-5-ethenyl-3,4-O-isopropylidenecyclopentanetetraol 、 (1S,2S,3S,4S,5S)-2-O-benzyl-5-ethenyl-3,4-O-isopropylidenecyclopentanetetraol
  参考文献：
  名称：

  Synthesis of 2-vinylcyclopentanols by SmI 2 /Pd(0) - promoted carbohydrate ring-contraction

  摘要：

  The treatment of methyl 5-vinylpyranosides with SmI2/cat. Pd(0) results in the formation of 2-vinylcyclopentanols. This process represents a new direct transformation of a carbohydrate structure into a functionalized carbocycle. The salient feature of this reaction is the preferred trans-relationship observed between the newly created stereocenters which is opposite to that found with alternative methodology. Moderate diastereoselectivities combined with high chemical yields provide preparatively useful yields of the major carbocyclic trans-diastereomer. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00317-7
• 作为产物：
  描述：

  methyl 3,4-di-O-isopropylidene-β-D-galactopyranoside 在 吡啶 、 正丁基锂 、 草酰氯 、 四丁基氟化铵 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.5h， 生成 methyl 2-O-benzyl-6,7-dideoxy-3,4-O-isopropylidene-β-D-galacto-hept-6-enopyranoside
  参考文献：
  名称：

  SmI2 / Pd（0）促进碳水化合物环收缩合成乙烯基和炔基环戊四醇。

  摘要：

  由对映体纯的形式，由适当的碳水化合物前体以对映体纯的形式，通过SmI2和催化的Pd（O）促进的直接一步式环缩过程制备各种乙烯基或炔基取代的多羟基化环戊烷和环丁烷。该反应被认为是通过中间的开环的烯丙基或烯丙基complex络合物进行的，该络合物通过分子内羰基加成而发生闭环。在两个新创建的立体异构中心发现乙烯基（或炔基）和羟基之间存在主要的反式关系，在形成高炔丙基环戊醇产物中观察到良好的立体选择性。在适当的条件下，使用替代方法无法直接获得立体异构体的制备有用的产量。

  DOI：

  10.1021/jo0005619

文献信息

• Direct carbohydrate to carbocycle conversions via intramolecular allylation with Et2Zn/Pd(0)
  作者：José M Aurrecoechea、Mónica Arrate、Jesús H Gil、Beatriz López

  DOI：10.1016/s0040-4020(03)00825-1

  日期：2003.7

  Treatment of 5-vinylpyranosides with Et2Zn and catalytic Pd(0), in the presence of ZnCl2, results in the formation of 5-membered carbocyclic products. This carbohydrate ring-contraction features an intramolecular allylation of a ring-opened carbohydrate aldehyde by an in situ-generated nucleophilic allylzinc species. The stereoselectivity about vinyl and free hydroxyl groups at the newly created stereogenic centers varies from low to moderate while both its extent and sense are found to depend on particular structural features (e.g. the configuration of the starting carbohydrate). (C) 2003 Elsevier Science Ltd. All rights reserved.
• Synthesis of Vinyl- and Alkynylcyclopentanetetraols by SmI₂/Pd(0)-Promoted Carbohydrate Ring-Contraction
  作者：José M. Aurrecoechea、Beatriz López、Mónica Arrate

  DOI：10.1021/jo0005619

  日期：2000.10.1

  predominant trans relationship is found between vinyl (or alkynyl) and hydroxyl groups at the two newly created stereogenic centers, with good to excellent levels of stereoselectivity being observed in the formation of homopropargyl cyclopentanol products. Under appropriate conditions, preparatively useful yields are realized of stereoisomers not directly available using alternative methodology.

  由对映体纯的形式，由适当的碳水化合物前体以对映体纯的形式，通过SmI2和催化的Pd（O）促进的直接一步式环缩过程制备各种乙烯基或炔基取代的多羟基化环戊烷和环丁烷。该反应被认为是通过中间的开环的烯丙基或烯丙基complex络合物进行的，该络合物通过分子内羰基加成而发生闭环。在两个新创建的立体异构中心发现乙烯基（或炔基）和羟基之间存在主要的反式关系，在形成高炔丙基环戊醇产物中观察到良好的立体选择性。在适当的条件下，使用替代方法无法直接获得立体异构体的制备有用的产量。
• Synthesis of 2-vinylcyclopentanols by SmI 2 /Pd(0) - promoted carbohydrate ring-contraction
  作者：JoséM. Aurrecoechea、Beatriz López

  DOI：10.1016/s0040-4039(98)00317-7

  日期：1998.4

  The treatment of methyl 5-vinylpyranosides with SmI2/cat. Pd(0) results in the formation of 2-vinylcyclopentanols. This process represents a new direct transformation of a carbohydrate structure into a functionalized carbocycle. The salient feature of this reaction is the preferred trans-relationship observed between the newly created stereocenters which is opposite to that found with alternative methodology. Moderate diastereoselectivities combined with high chemical yields provide preparatively useful yields of the major carbocyclic trans-diastereomer. (C) 1998 Elsevier Science Ltd. All rights reserved.