7-oxobicyclo[2.2.1]heptane-2,3-dicarboxylic acid dimethyl ester | 128708-56-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 7-oxobicyclo[2.2.1]heptane-2,3-dicarboxylic acid dimethyl ester
• 英文别名: dimethyl (1S,2R,3S,4R)-7-oxobicyclo[2.2.1]heptane-2,3-dicarboxylate
• CAS: 128708-56-5
• 化学式: C₁₁H₁₄O₅
• 分子量: 226.229
• InChiKey: GOJMKUVROKURLQ-SOSBWXJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  7-oxobicyclo[2.2.1]heptane-2,3-dicarboxylic acid dimethyl ester 在 sodium hydroxide 、 sodium tetrahydroborate 、 mercury(II) diacetate 、 sodium tert-pentoxide 作用下， 反应 5.0h， 生成 (1S,2R,3S,4R,7S)-7-Hydroxy-7-methyl-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Electronic control of π-facial diastereoselection. Electrophilic additions to 7-methylenenorbornanes

  摘要：

  可通过电子修饰2,3-内型、内型取代基，远程控制亲电体对空间无偏向的7-亚甲基降冰片烷2a-c的接近。

  DOI：

  10.1039/c39910000018
• 作为产物：
  描述：

  endo-10,10-dimethoxy-4-oxatricyclo[5.2.1.02,6]decane-3,5-dione 在 硫酸 、 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 7.5h， 生成 7-oxobicyclo[2.2.1]heptane-2,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Mehta, Goverdhan; Khan, Faiz Ahmed, Journal of the American Chemical Society, 1990, vol. 112, # 16, p. 6140 - 6142

  摘要：

  DOI：

文献信息

• Biooxidation of Bridged Cycloketones Using Baeyer−Villiger Monooxygenases of Various Bacterial Origin
  作者：Radka Snajdrova、Ingbert Braun、Thorsten Bach、Kurt Mereiter、Marko D. Mihovilovic

  DOI：10.1021/jo701704x

  日期：2007.12.1

  synthesized and utilized as substrates to study biooxidations mediated by Baeyer−Villiger monooxygenases (BVMO) of various bacterial origin. The required enzymes were heterologously produced by recombinant overexpression systems based on Escherichia coli to enable facile recycling of the required nicotinamide cofactors during the whole-cell biotransformations. Ketone precursors of various structural demands

  合成了桥联的环酮，并将其用作底物，以研究由多种细菌来源的拜尔-维利格单加氧酶（BVMO）介导的生物氧化。所需的酶是通过基于大肠杆菌的重组过表达系统异源产生的以在全细胞生物转化过程中轻松回收所需的烟酰胺辅因子。选择具有各种结构要求的酮前体来评估BVMOs活性位点的空间限制和灵活性。通过前手性底物的不对称化，在单个生物氧化步骤中产生了四个到六个立体异构中心。本研究中研究的酶文库在某些情况下允许获得对映体选择性优异的对映内酯产品。结合独特的底物接受特性，这项研究中获得的生物转化结果支持了最近提议的分为两类环酮转化BVMO的分类。
• Modification of π-face selectivity of 7-norbornenones during reduction in β-cyclodextrin and solid state
  作者：Goverdhan Mehta、Faiz Ahmed Khan、K.Ananda Lakshmi

  DOI：10.1016/s0040-4039(00)74793-9

  日期：1992.12

  Electronically/electrostatically dictated face-selection in -substituted 7-norbornenones can be altered/reversed by means of host-guest interaction with β-CD. Reversal in face-selectivity is also observed in the reduction of 5,6-, -substituted 7-norbornenone in solid state.

  可以通过宿主-客体与β-CD的相互作用来改变/逆转被取代的7-降冰片烯酮中电子/静电决定的面部选择。在固态下的5，6- ，-取代的7-降冰片烯酮的还原中也观察到面选择性的逆转。
• Importance of orbital and electrostatic interactions in determining π-facial selectivities in nucleophilic additions to endo-substituted bicyclo[2.2.2]octan-2-ones
  作者：Goverdhan Mehta、Faiz Ahmed Khan、Bishwajit Ganguly、Jayaraman Chandrasekhar

  DOI：10.1039/c39920001711

  日期：——

  The diastereoselectivities in nucleophilic additions to bicyclo[2.2.2]octan-2-ones can be modulated by distal endo-substituents; both orbital and electrostatic interactions contribute to the observed stereoselectivity.

  双环[2.2.2] octan-2-one的亲核加成中的非对映选择性可以通过远端内位取代基来调节。轨道和静电相互作用都有助于观察到的立体选择性。
• A simple computational model for predicting .pi.-facial selectivity in reductions of sterically unbiased ketones. Relative importance of electrostatic and orbital interactions
  作者：Bishwajit Ganguly、Jayaraman Chandrasekhar、Faiz Ahmed Khan、Goverdhan Mehta

  DOI：10.1021/jo00059a022

  日期：1993.3

  Various factors controlling the preferred facial selectivity in the reductions of a number of sterically unbiased ketones have been evaluated using a semiempirical MO procedure. MNDO optimized geometries do not reveal any significant ground-state distortions which can be correlated with the observed face selectivities. Electrostatic effects due to an approaching reagent were modeled by placing a test negative charge at a fixed distance from the carbonyl carbon on each of the two faces. A second series of calculations was carried out using the hydride ion as a test nucleophile. The latter calculations effectively include orbital interactions involving the sigma and sigma* orbitals of the newly formed bond in the reaction. The computed energy differences with the charge model are generally much larger compared to those with the hydride ion. However, both models lead to predictions which are qualitatively consistent with the experimentally determined facial preferences for most of the systems. Thus, electrostatic interactions between the nucleophile and the substrate seem to effectively determine the face selectivities in these molecules. However, there are a few exceptions in which orbital interactions are found to contribute significantly and occasionally reverse the preference dictated by electrostatic effects. The remarkable success of the hydride model calculations, in spite of retaining the unperturbed geometries of the substrates, points to the unimportance of torsional effects and orbital distortions associated with the pyramidalized carbonyl unit in the transition state in most of the substrates considered. Additional experimental results are reported which provide useful calibration for the present computational approach.
• Mehta, Goverdhan; Khan, Faiz Ahmed, Journal of the American Chemical Society, 1990, vol. 112, # 16, p. 6140 - 6142
  作者：Mehta, Goverdhan、Khan, Faiz Ahmed

  DOI：——

  日期：——