(-)-(1R,2R,6R,7S)-5-oxo-endo-tricyclo<5.2.1.0^2,6>dec-8-ene-2-carboxylic acid | 157457-55-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(1R,2R,6R,7S)-5-oxo-endo-tricyclo<5.2.1.0^2,6>dec-8-ene-2-carboxylic acid
• 英文别名: (1R,2R,6R,7S)-5-oxotricyclo[5.2.1.02,6]dec-8-ene-2-carboxylic acid
• CAS: 157457-55-1
• 化学式: C₁₁H₁₂O₃
• 分子量: 192.214
• InChiKey: XMUBESDJFKRCNW-VFYMIVFZSA-N

物化性质

• 沸点：
  375.7±42.0 °C(predicted)
• 密度：
  1.410±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-(1R,2R,6R,7S)-5-oxo-endo-tricyclo<5.2.1.0^2,6>dec-8-ene-2-carboxylic acid 在 氢氧化钾 、 草酰氯 、 三氯溴甲烷 、 2-mercaptopyridine-1-oxide sodium salt 、 N,N-二甲基甲酰胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 3.08h， 生成 (-)-(1S,2R,6R,7R)-methyl 3-hydroxy-6-methoxy-endo-tricyclo<5.2.1.02,6>dec-3,8-diene-4-carboxylate
  参考文献：
  名称：

  Total synthesis of (−)-kjellmanianone from tricyclodecadienone. A revision of its absolute configuration

  摘要：

  A stereocontrolled total synthesis of the naturally occurring cyclopentenoid (-)-kjellmanianone (8) under bar has been accomplished starting from enantiopure (+)-tricyclo[5.2.1.0(2,6)]decadienone 2-carboxylic ester (5) under bar. Key steps in this approach to (8) under bar include Barton's halodecarboxylation of <(17)under bar> followed by methoxylation to produce <(20)under bar>, nucleophilic epoxidation of enolacetate <(26)under bar> to introduce the alpha-hydroxyketone moiety and thermal fragmentation of <(27)under bar> using flash vacuum thermolysis (FVT) to give (8) under bar. The R configuration of synthetic (-)-kjellmanianone was unequivocally established by an X-ray diffraction analysis of its precursor <(27)under bar>: implying that the previously assigned absolute configuration of(+)-kjellmanianone is incorrect.

  DOI：

  10.1016/s0040-4020(01)89599-5
• 作为产物：
  描述：

  (3aS,4S,7R,7aS)-1-Oxo-1,4,7,7a-tetrahydro-4,7-methano-indene-3a-carboxylic acid ethyl ester 在 sodium hydroxide 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 (-)-(1R,2R,6R,7S)-5-oxo-endo-tricyclo<5.2.1.0^2,6>dec-8-ene-2-carboxylic acid
  参考文献：
  名称：

  （-）-kjellmanianone的立体特异性全合成及其绝对构型的修订

  摘要：

  从三环[5.2.1.0 2,6 ]癸二烯酮2-羧酸酯开始，完成了对自然存在的jjellmanianoneone的完全立体控制的全合成。该方法的关键步骤包括Barton的卤代羧化方法，亲核环氧化以引入羟基，并最终通过使用快速真空热解进行环还原。通过对其前体的X射线衍射分析明确地确定了合成（-）-kjellmanianone的R构型，这意味着需要修改以前分配的（+）-kjellmanianone的绝对构型。

  DOI：

  10.1016/s0040-4039(00)77033-x

文献信息

• A facile approach to norbornene-annulated cyclopentenones, a novel class of tricyclodecadienones
  作者：Jie Zhu、Antonius J.H Klunder、Binne Zwanenburg

  DOI：10.1016/0040-4020(95)98708-p

  日期：1995.4

  An efficient synthesis of norbornene annulated cyclopentenones and starting from readily available tricyclodecadienone carboxylic acid is described. Parent tricyclo[5.2.1.02,6]decadi-2(6),8-ene , an hitherto unknown compound, has been obtained in good yield by subjecting bromide to base induced elimination or by oxidative deselenylation of . 5-Substituted analogues are conveniently obtained from phenylselenide

  描述了降冰片烯环化的环戊烯酮的有效合成，并从容易获得的三环癸二烯酮羧酸开始。母体三环[5.2.1.0 2,6 ]癸二-2（6），8-烯（一种迄今未知的化合物）已通过使溴化物进行碱诱导的消除或氧化的脱硒基化反应以高收率获得。通过立体选择性共轭铜酸盐的添加，然后氧化消除硒基，可以从苯硒化物中方便地获得5-取代的类似物。环氧溴化物的脱氢溴化作用提供了降冰片烯环化的环戊二烯酮，该环戊二烯酮可在应变C上立即进行立体选择性1,4加成生成2 –C 6烯酮部分。这些新颖的降冰片烯环化的环戊烯酮可以被认为是2-环戊炔酮的合成等同物。
• Total synthesis of (−)-kjellmanianone from tricyclodecadienone. A revision of its absolute configuration
  作者：Jie Zhu、Antonius J.H. Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4020(01)89599-5

  日期：1994.1

  A stereocontrolled total synthesis of the naturally occurring cyclopentenoid (-)-kjellmanianone (8) under bar has been accomplished starting from enantiopure (+)-tricyclo[5.2.1.0(2,6)]decadienone 2-carboxylic ester (5) under bar. Key steps in this approach to (8) under bar include Barton's halodecarboxylation of <(17)under bar> followed by methoxylation to produce <(20)under bar>, nucleophilic epoxidation of enolacetate <(26)under bar> to introduce the alpha-hydroxyketone moiety and thermal fragmentation of <(27)under bar> using flash vacuum thermolysis (FVT) to give (8) under bar. The R configuration of synthetic (-)-kjellmanianone was unequivocally established by an X-ray diffraction analysis of its precursor <(27)under bar>: implying that the previously assigned absolute configuration of(+)-kjellmanianone is incorrect.
• Stereospecific total synthesis of (−)-kjellmanianone and a revision of its absolute configuration
  作者：Jie Zhu、Antonius J.H. Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4039(00)77033-x

  日期：1994.4

  of naturally occurring kjellmanianone has been accomplished starting from tricyclo[5.2.1.02,6]decadienone 2-carboxylic ester . The key steps in this approach to include Barton's halodecarboxylation methodology, nucleophilic epoxidation to introduce the hydroxy group and ultimately, a cycloreversion by using flash vacuum thermolysis. The R configuration of synthetic (−)-kjellmanianone was unequivocally

  从三环[5.2.1.0 2,6 ]癸二烯酮2-羧酸酯开始，完成了对自然存在的jjellmanianoneone的完全立体控制的全合成。该方法的关键步骤包括Barton的卤代羧化方法，亲核环氧化以引入羟基，并最终通过使用快速真空热解进行环还原。通过对其前体的X射线衍射分析明确地确定了合成（-）-kjellmanianone的R构型，这意味着需要修改以前分配的（+）-kjellmanianone的绝对构型。