ethyl 5-oxo-tricyclo<5.2.1.0^2,6>deca-8-ene-2-carboxylate | 119347-64-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 5-oxo-tricyclo<5.2.1.0^2,6>deca-8-ene-2-carboxylate
• 英文别名: ethyl 5-oxo-tricyclo[5.2.1.0^2,6]deca-8-ene-2-carboxylate；ethyl (1R,2R,6R,7S)-5-oxotricyclo[5.2.1.02,6]dec-8-ene-2-carboxylate
• CAS: 119347-64-7
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: JEPWDUCFWDEIQY-UPBCOZELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 5-oxo-tricyclo<5.2.1.0^2,6>deca-8-ene-2-carboxylate 在 氢氧化钾 、 sodium hydroxide 、 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 、 甲醇 为溶剂， 反应 7.08h， 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：

  ethyl 5-oxo-tricyclo[5.2.1.0.]deca-3,8-diene-2-carboxylate 在 sodium tetrahydroborate 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醇 为溶剂， 反应 3.25h， 生成 ethyl 5-oxo-tricyclo<5.2.1.0^2,6>deca-8-ene-2-carboxylate
  参考文献：
  名称：

  Ghosh, Sunil K.; Satapathi, Tushar K.; Rao, P. S. V. Subba, Synthetic Communications, 1988, vol. 18, # 15, p. 1883 - 1890

  摘要：

  DOI：

文献信息

• 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。
• Facial selectivity in addition reactions to the highly strained enone in tricyclo[5.2.1.02,6]deca-2(6),8-dienone and tricyclo[5.2.1.02,6]dec-2(6)-enone
  作者：Antonius J.H. Klunder、Andries A. Volkers、Binne Zwanenburg

  DOI：10.1016/j.tet.2009.01.012

  日期：2009.3

  Tricyclo[5.2.1.02,6]deca-2(6),8-dien-3-one contains a highly strained central double bond due to geometrical constraints imposed by the tricyclic skeleton which does not allow optimal sp2 hybridization at the C2 and C6 bridgehead positions. Michael addition of various nucleophiles (alkoxides, cyanide, and malonate) under protic conditions resulted in an exclusive exo-facial selectivity. This preference

  三环[5.2.1.0 2,6 ] deca-2（6），8-dien-3-one包含高应变中心双键，这是由于三环骨架施加的几何约束，不允许在C处进行最佳的sp 2杂交2和C 6桥头位置。迈克尔加成各种亲核（醇盐，氰化物，和丙二酸二甲酯）质子条件下导致了异外-facial选择性。这种偏爱可以通过空间和电子因素来解释。使用二烷基铜酸锂的迈克尔加成导致形成内产物的主要部分，但也获得了一些外产物。这些exo产品来自内吞法可能是铜酸盐与烯酮部分和烯属C 8 -C 9键配位的结果。Michael加成到三环[5.2.1.0 2,6 ]癸-2-（6） -烯-3-酮，它缺乏该C 8 -C 9双键表明独家外-facial选择性，得到外-products。除此之外，这些添加物都比三环[5.2.1.0 2,6 ] deca-2（6），8-dien-3-one慢得多，这证明了C 8 –C 9双键在与该反应中的显着电子参与。基质。
• 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.
• Ghosh, Sunil K.; Satapathi, Tushar K.; Rao, P. S. V. Subba, Synthetic Communications, 1988, vol. 18, # 15, p. 1883 - 1890
  作者：Ghosh, Sunil K.、Satapathi, Tushar K.、Rao, P. S. V. Subba、Sarkar, Tarun

  DOI：——

  日期：——