7-Spirocyclopropanbicyclo[2.2.1]hept-5-en-2,3-dion | 60526-40-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7-Spirocyclopropanbicyclo[2.2.1]hept-5-en-2,3-dion
• 英文别名: Spiro(bicyclo(2.2.1)hept-5-ene-7,1'-cyclopropane)-2,3-dione；spiro[bicyclo[2.2.1]hept-5-ene-7,1'-cyclopropane]-2,3-dione
• CAS: 60526-40-1
• 化学式: C₉H₈O₂
• 分子量: 148.161
• InChiKey: SRQNBAJQPIQHQU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7-Spirocyclopropanbicyclo[2.2.1]hept-5-en-2,3-dion 在 正丁基锂 、 potassium diazodicarboxylate 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 130.0h， 生成
  参考文献：
  名称：

  Consequences of Modulated Precompression along Reaction Coordinates. Synthesis, Crystallographic Structural Studies, and Rate of Intramolecular Dyotropy in an Extended Series of syn-Sesquinorbornene Disulfones

  摘要：

  In order to produce a broad range of syn-sesquinorbornene disulfones, (Z)-1,2-bis(phenylsulfonyI)ethylene was added in Diels-Alder fashion (high-pressure conditions) to tricyclo[5.2.1.0(2.6)]deca-2,5,8-trienes carrying isopropylidene or spirocyclopropane subunits at one or two sites. The central double bond in these adducts was then regiospecifically reduced with diimide, epoxidized with MCPBA, or cyclopropanated by [3 + 2] cycloaddition with diazomethane and subsequent photoinduced nitrogen extrusion. Each product in ah-three series was subjected to X-ray crystallographic analysis in order to quantify in the solid state the distance which each endo alpha-sulfonyl proton is required to traverse during dyotropic migration to the proximal norbornene double bond. The kinetics of these isomerizations were also determined, a relative reactivity scale was realized, and the values of k(ref) at 160 degrees C were found not to correlate well with the average distance across the intracavity gap. Although proximity of the reaction centers is clearly a prerequisite for smooth operation of the dyotropic shifts, modulation of this distance is not the sole contributor to reaction rate. Rather, the data are in agreement with the working hypothesis that various levels of steric compression within these disulfones facilitate passage over the relevant transition state to a greater or lesser degree depending on the magnitude of these nonbonded interactions.

  DOI：

  10.1021/ja00103a004

文献信息

• Formation of non-racemic E- and Z-olefins based on discrimination of enantiotopic carbonyl groups in α-diketones by a chiral phosphonate reagent
  作者：Kiyoshi Tanaka、Toshiyuki Watanabe、Yoshihisa Ohta、Kaoru Fuji

  DOI：10.1016/s0040-4039(97)10328-8

  日期：1997.12

  A chiral HWE reagent reacted with an alternative carbonyl group of meso-alpha-diketones of bicyclo[2.2.1] system to give non-racemic (Z)- and (E)-olefins, respectively. (C) 1997 Elsevier Science Ltd.
• Consequences of Modulated Precompression along Reaction Coordinates. Synthesis, Crystallographic Structural Studies, and Rate of Intramolecular Dyotropy in an Extended Series of syn-Sesquinorbornene Disulfones
  作者：George A. O'Doherty、Robin D. Rogers、Leo A. Paquette

  DOI：10.1021/ja00103a004

  日期：1994.11

  In order to produce a broad range of syn-sesquinorbornene disulfones, (Z)-1,2-bis(phenylsulfonyI)ethylene was added in Diels-Alder fashion (high-pressure conditions) to tricyclo[5.2.1.0(2.6)]deca-2,5,8-trienes carrying isopropylidene or spirocyclopropane subunits at one or two sites. The central double bond in these adducts was then regiospecifically reduced with diimide, epoxidized with MCPBA, or cyclopropanated by [3 + 2] cycloaddition with diazomethane and subsequent photoinduced nitrogen extrusion. Each product in ah-three series was subjected to X-ray crystallographic analysis in order to quantify in the solid state the distance which each endo alpha-sulfonyl proton is required to traverse during dyotropic migration to the proximal norbornene double bond. The kinetics of these isomerizations were also determined, a relative reactivity scale was realized, and the values of k(ref) at 160 degrees C were found not to correlate well with the average distance across the intracavity gap. Although proximity of the reaction centers is clearly a prerequisite for smooth operation of the dyotropic shifts, modulation of this distance is not the sole contributor to reaction rate. Rather, the data are in agreement with the working hypothesis that various levels of steric compression within these disulfones facilitate passage over the relevant transition state to a greater or lesser degree depending on the magnitude of these nonbonded interactions.