exo-cis-Bicyclo<2.2.1>-5-hepteno-2,3-dimethylol-ditosylat | 70116-05-1

• 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: exo-cis-Bicyclo<2.2.1>-5-hepteno-2,3-dimethylol-ditosylat
• 英文别名: endo-cis-Bicyclo<2.2.1>-5-hepteno-2,3-dimethylol-ditosylat；5endo,6endo-bis-(toluene-4-sulfonyloxymethyl)-norborn-2-ene；5endo,6endo-Bis-(toluol-4-sulfonyloxymethyl)-norborn-2-en；5,6-Bis(endo-p-toluenesulfonyloxymethyl)-bicyclo[2.2.1]hept-2-ene；[(1S,2R,3S,4R)-3-[(4-methylphenyl)sulfonyloxymethyl]-2-bicyclo[2.2.1]hept-5-enyl]methyl 4-methylbenzenesulfonate
• CAS: 70116-05-1
• 化学式: C₂₃H₂₆O₆S₂
• 分子量: 462.588
• InChiKey: AHVQTTLMPKRSCE-PVTAMDAMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  exo-cis-Bicyclo<2.2.1>-5-hepteno-2,3-dimethylol-ditosylat 在 lithium aluminium tetrahydride 、 lithium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 endo-2,3-dimethyl-5-norbornene
  参考文献：
  名称：

  Cycloaddition. XII. Photosensitized cycloaddition of the cis- and trans-2-butenes to cyclopentadiene

  摘要：

  DOI：

  10.1021/ja00766a046
• 作为产物：
  描述：

  (1R,2S,3R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dimethanol 以88%的产率得到
  参考文献：
  名称：

  NAGAO, YOSHIMITSU;INOUE, TAKEHISA;FUJITA, EIICHI;TERADA, SHUNJI;SHIRO, MO+, TETRAHEDRON, 1984, 40, N 8, 1215-1223

  摘要：

  DOI：

文献信息

• Structure-reactivity relations for thiol-disulfide interchange
  作者：Janette Houk、George M. Whitesides

  DOI：10.1021/ja00256a040

  日期：1987.10

  di- and trithiols and the disulfides derived from either 2-mercaptoethanol or dithiothreitol. Reactions were conducted in methanol-d,/aqueous buffer (pH 7) or methanold, at 25 "C, using NMR spectroscopy to follow the reactions. These data were used to rank the dithiols in terms of reduction potential and to infer the structure of the disulfides formed from them on oxidation. There is a general correlation

  平衡常数由 36 个二硫醇和三硫醇与衍生自 2-巯基乙醇或二硫苏糖醇的二硫化物之间的硫醇-二硫化物交换确定。反应在甲醇-d/水性缓冲液 (pH 7) 或甲醇中进行，在 25°C 下，使用 NMR 光谱跟踪反应。这些数据用于根据还原电位对二硫醇进行排序并推断其结构氧化时由它们形成的二硫化物。二硫醇的还原能力与氧化时形成的含二硫化物环的大小之间存在普遍的相关性：形成六元环的二硫醇还原性最强（K = 103-105 M 相对于氧化的 2-巯基乙醇）；五元和七元环的还原性降低约 1 个数量级。类似于 1 的化合物，2-乙二硫醇在相对稀释的溶液 (- 1 mM) 中形成环状双（二硫化物）二聚体，但在较高浓度下聚合。其他类别的二硫醇在氧化时形成聚合物。
• Baeyer-Villiger Oxidation of Bridged<i>endo-</i>Tricyclic Ketones with Engineered<i>Escherichia coli</i>Expressing Monooxygenases of Bacterial Origin
  作者：Marko D. Mihovilovic、Radka Snajdrova、Alexander Winninger、Florian Rudroff

  DOI：10.1055/s-2005-918938

  日期：——

  Whole-cell biotransformations using engineered strains of Escherichia coli expressing cyclopentanone (CPMO) and cyclohexanone monooxygenases (CHMO) of various bacterial origins have been tested for substrate acceptance ontricyclic ketones. Based on the stereopreference of the biocatalytic Baeyer-Villiger oxidation, our recent clustering of this library of enzymes into two distinct groups based on protein

  使用表达各种细菌来源的环戊酮 (CPMO) 和环己酮单加氧酶 (CHMO) 的大肠杆菌工程菌株进行的全细胞生物转化已被测试用于底物接受三环酮。基于生物催化 Baeyer-Villiger 氧化的立体偏好，我们最近根据蛋白质序列将该酶库聚类为两个不同的组。连同用于生产底物酮的短而容易的反应序列，微生物生物氧化能够获得对足产物内酯，作为天然产物和生物活性化合物合成中的通用构件。
• Selective Hydrogen Chloride Elimination from Primary Chlorides Induced by the Fluoride Anion. Anchimeric participation of the chloromethyl group in the heterolytic opening of an epoxide. Stereospecific syntheses of 5,6-bis (methylidene)-syn-2-norbornen-7-ol and 5,6-bis (methylidene)-endo-3-chloro-exo-2-norbornanol
  作者：Andr� Chollet、Jean-Pierre Hagenbuch、Pierre Vogel

  DOI：10.1002/hlca.19790620218

  日期：1979.3.7

  exo-6-bis (chloromethyl)-exo-2, 3-epoxynorbornane (5). The Wagner-Meerwein rearrangement was precluded in these reactions probably because of the formation of a relatively stable chloronium ion 15 arising from the participation of the 1,4-chlorine atom of the endo-5-chloromethyl group in the heterolytic ring opening of the epoxide 5.

  给出了醇10和18以及相应的酮11和19的合成。内基-5，外基-6-双（氯甲基）-内基-3-氯-外基-2-降冰片醇（16）和内基-5-（溴甲基）-外基-6-（氯甲基）-内基-3-氯-外型-2-降冰片烷醇（17通过HCl-和分别获得），的HBr加成到远藤-5，外切-6-双（氯甲基） -外-2,3-环氧降冰片烷（5）。这瓦格纳米尔文重排在这些反应可能是因为相对稳定的氯鎓离子形成的排除15从的1,4-氯原子的参与产生内切在环氧化物的异裂开环基氯-5 5。
• Self‐Immobilizing Precatalysts: Norbornene‐Bridged Zirconium<i>ansa‐</i>Metallocenes
  作者：Eleonora Polo、Fabrizio Forlini、Valerio Bertolasi、Antonella Caterina Boccia、Maria Carmela Sacchi

  DOI：10.1002/adsc.200800168

  日期：2008.7.7

  AbstractWe report here the synthesis of new tethered biscyclopentadienyl and bisindenyl zirconocenes, bearing one unsaturation on the interannular bridge, and their use as self‐immobilizing catalysts. They proved to be active catalysts towards ethylene polymerization in solution, with activities comparable to those displayed by commercial rac‐Et(Ind)2ZrCl2. When tested as self‐polymerization catalysts under suitable experimental conditions, they gave colored precipitates that, once reactivated with MAO, were significantly active in ethylene polymerization, although lower than those of the corresponding catalytic systems in solution. The molecular weights of the produced polymers were similar to those obtained with the same catalysts in solution, but their distribution resulted to be broader, with values typical of heterogeneous catalytic systems. From 13C NMR studies we had the first spectroscopic evidence of the actual incorporation of a metallocene of this type into a polymeric chain.
• A new nonenzymatic chiral induction into prochiral meso compounds
  作者：Yoshimitsu nagao、Takemsa inoue、Eiichi fujita、Shunji Terada、Motoo shiro

  DOI：10.1016/s0040-4020(01)82408-x

  日期：——