(3aS,4S,7R,7aS)-1-Oxo-1,4,7,7a-tetrahydro-4,7-methano-indene-3a-carboxylic acid ethyl ester | 129569-55-7

• 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: (3aS,4S,7R,7aS)-1-Oxo-1,4,7,7a-tetrahydro-4,7-methano-indene-3a-carboxylic acid ethyl ester
• 英文别名: ethyl (1S,2S,6S,7R)-5-oxotricyclo[5.2.1.02,6]deca-3,8-diene-2-carboxylate
• CAS: 129569-55-7
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: ZYKKBCZKDGUTCM-JQEKQURRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  (3aS,4S,7R,7aS)-1-Oxo-1,4,7,7a-tetrahydro-4,7-methano-indene-3a-carboxylic acid ethyl ester 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以84%的产率得到1,4,7,7aα-tetrahydro-1-oxo-4α,7α-methano-3aH-indene-(3aR)-3aα-carboxylic acid
  参考文献：
  名称：

  Studies in the synthesis of the thromboxane receptor antagonist EP 092 and its enantiomers

  摘要：

  DOI：

  10.1021/jo00310a017
• 作为产物：
  描述：

  ethyl 5-oxo-tricyclo[5.2.1.0.]deca-3,8-diene-2-carboxylate 在 porcine liver esterase 、 sodium hydroxide 、 potassium dihydrogenphosphate 作用下， 以 乙腈 为溶剂， 反应 22.0h， 生成 1,4,7,7aα-tetrahydro-1-oxo-4α,7α-methano-3aH-indene-(3aR)-3aα-carboxylic acid 、 (1R,2R,6R,7S)-5-oxotricyclo[5.2.1.02,6]deca-3,8-diene-2-carboxylic acid 、 (3aS,4S,7R,7aS)-1-Oxo-1,4,7,7a-tetrahydro-4,7-methano-indene-3a-carboxylic acid ethyl ester
  参考文献：
  名称：

  Studies in the synthesis of the thromboxane receptor antagonist EP 092 and its enantiomers

  摘要：

  DOI：

  10.1021/jo00310a017

文献信息

• A stereo- and enantioselective approach to clavulones from tricyclodecadienone using flash vacuum thermolysis
  作者：Jie Zhu、Ji-Ying Yang、Antonius J.H Klunder、Zhi-Yu Liu、Binne Zwanenburg

  DOI：10.1016/0040-4020(95)00237-3

  日期：1995.5

  which are key intermediates in this approach, are obtained from enantiopure endo-tricyclo[5.2.1.02,6]decadienones (+)- and (+)- in 6 and 8 steps, respectively. Crucial steps are the reductive epoxy ring opening in compounds (+)- and to give the corresponding diols (+)- and , and the thermal cycloreversion of tricyclodecenones (+)- and , using the technique of flash vacuum thermolysis (FVT). The synthesis

  描述了克拉维酮及其类似物的立体和对映选择性合成。γ-羟基环戊烯酮（-）-和-是该方法的关键中间体，分别从对映体纯的内-三环[5.2.1.0 2,6 ]癸二烯酮（+）-和（+）-分别以6和8个步骤获得。关键步骤是使用闪蒸真空热解（FVT）技术在化合物（+）-中还原环氧环，从而得到相应的二醇（+）-和，以及三环癸烯酮（+）-和热环还原。对映体（-）-的合成代表克拉维酮的正式全合成。克拉维酮类似物（-）-和（-）- （X = CH 2 OH）的合成是通过与醛缩合，然后除去水并去除保护性THP-基团来完成的。
• 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。
• Enzymic optical resolution and flash vacuum thermolysis in concert for the synthesis of optically active cyclopentenones
  作者：A.J.H. Klunder、W.B. Huizinga、P.J.M. Sessink、B. Zwanenburg

  DOI：10.1016/s0040-4039(00)95729-0

  日期：1987.1
• 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.
• GARLAND, ROBERT B.;MIYANO, MASATERU;PIREH, DAISY;CLARE, MICHAEL;FINNEGAN,+, J. ORG. CHEM., 55,(1990) N3, C. 5854-5861
  作者：GARLAND, ROBERT B.、MIYANO, MASATERU、PIREH, DAISY、CLARE, MICHAEL、FINNEGAN,+

  DOI：——

  日期：——