(-)-(1R,2S,6R,7S,2'S)-5-(2'-hydroxymethylpyrrolidin-1'-yl)-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one | 185542-14-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (-)-(1R,2S,6R,7S,2'S)-5-(2'-hydroxymethylpyrrolidin-1'-yl)-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one
• 英文别名: (1R,2S,6R,7S,2'S)-5-(2'-hydroxymethylpyrrolidin-1'-yl)-endo-tricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one；(1R,2S,6R,7S)-5-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]tricyclo[5.2.1.02,6]deca-4,8-dien-3-one
• CAS: 185542-14-7
• 化学式: C₁₅H₁₉NO₂
• 分子量: 245.321
• InChiKey: ICJGCAFXIOXSSV-YRRINSJYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-(1R,2S,6R,7S,2'S)-5-(2'-hydroxymethylpyrrolidin-1'-yl)-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one 在 lithium aluminium tetrahydride 、 氢氧化钾 作用下， 以 四氢呋喃 为溶剂， 反应 2.25h， 以71%的产率得到(1R,2S,6R,7S)-tricyclo[5.2.1.0(2,6)]deca-4,8-dien-3-one
  参考文献：
  名称：

  伪的不对称desymmetrization内消旋5-羟基-内三环[5.2.1.0 2,6 ]癸-4,8-二烯-3-酮

  摘要：

  从容易获得的伪内消旋-5-羟基-内环-三环[5.2.1.0 2,6 ] deca-4,8-​​dien-3-one开始，已经完成了通往对映体纯的内-三环癸二烯酮系统的新途径。使用（S）-脯氨醇或其甲基醚进行的不对称化以高收率和50％的de产生相应的烯胺酮。非对映异构体的完全分离已通过其乙酸盐方便地实现。主要的非对映异构体的绝对立体化学是通过单晶X射线衍射分析确定的。用氢化锂铝对手性助剂的还原消除以良好的总收率提供了光学纯的母体三环癸二烯酮。

  DOI：

  10.1016/s0040-4020(01)01007-9
• 作为产物：
  描述：

  4-环戊烯-1,3-二酮 以 甲苯 为溶剂， 生成 (-)-(1R,2S,6R,7S,2'S)-5-(2'-hydroxymethylpyrrolidin-1'-yl)-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one
  参考文献：
  名称：

  一个的不对称desymmetrization伪-内消旋内三环[5.2.1.0 2,6 ]癸-4,8-二烯-3-酮通过手性胺

  摘要：

  于对映体纯的新型路线内-tricyclodecadienone系统已经实现了从容易获得原料的伪-内消旋-5-羟基-内三环[5.2.1.0 2,6 ]癸-4,8-二烯-3-酮4。的（±）动态动力学拆分- 4使用（S）-prolinol或其甲基醚通向相应烯胺酮部6b，C以高收率和以日的50％。6b的非对映异构体的完全分离可通过其乙酸酯方便地完成。主要非对映体的绝对立体显示是耳鼻喉科-6b。手性助剂在还原消除耳鼻喉科- -6b用氢化铝锂，得到旋光纯的父tricyclodecadienone（+）1良好总产率（X = H）。

  DOI：

  10.1016/0040-4039(96)01810-2

文献信息

• Asymmetric desymmetrization of a Pseudo-mesoendo-tricyclo[5.2.1.02,6]deca-4,8-dien-3-one by chiral amines
  作者：Frank J.A.D. Bakkeren、Namakkal G. Remesh、Debby de Groot、Antonius J.H. Klunder、Binne Zwanenburg

  DOI：10.1016/0040-4039(96)01810-2

  日期：1996.10

  ndo-tricyclo[5.2.1.02,6]deca-4,8-dien-3-one 4. Dynamic kinetic resolution of (±)-4 using (S)-prolinol or its methyl ether leads to the corresponding enaminones 6b,c in high yields and with a de of 50%. Complete separation of the diastereomers of 6b is conveniently accomplished via their acetates. The absolute stereochemistry of the major diastereomer was shown to be ent-6b. Reductive elimination of

  于对映体纯的新型路线内-tricyclodecadienone系统已经实现了从容易获得原料的伪-内消旋-5-羟基-内三环[5.2.1.0 2,6 ]癸-4,8-二烯-3-酮4。的（±）动态动力学拆分- 4使用（S）-prolinol或其甲基醚通向相应烯胺酮部6b，C以高收率和以日的50％。6b的非对映异构体的完全分离可通过其乙酸酯方便地完成。主要非对映体的绝对立体显示是耳鼻喉科-6b。手性助剂在还原消除耳鼻喉科- -6b用氢化铝锂，得到旋光纯的父tricyclodecadienone（+）1良好总产率（X = H）。
• An efficient regioselective halogenation of 5-amino-endo-tricyclo[5.2.1.02,6]deca-4,8-dien-3-ones
  作者：Namakkal G Ramesh、Erik H Heijne、Antonius J.H Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4020(01)01228-5

  日期：2002.2

  An effective regioselective halogenation of 5-arnino-endo-tricyclo decenyl enaminones 6 using N-halosuccinimides is reported. The reaction is extremely fast and the yields are almost quantitative. Exclusive alpha,N-dihalo or alpha,gamma-dihalo compounds can be obtained by tuning the reaction conditions. Facile transfer of bromine from alpha,N-dibromo enaminones 8 has been observed, A rationale for the formation of the various halogenated products is presented. The alpha,gamma-dihalo enaminones allow further functionalisation of the tricyclodecadienone system and thus are promising precursors for pharmacologically interesting halo-cyclopentanoids. More importantly, the otherwise more reactive norbornene double bond remained intact under these halogenation conditions. (C) 2002 Elsevier Science Ltd. All rights reserved.
• ——
  作者：René de Gelder、Jan M. M. Smits、Namakkal G. Ramesh、Frank J. A. D. Bakkeren、Antonius J. H. Klunder

  DOI：10.1023/a:1021781024782

  日期：——

  The crystal and molecular structure of(-)-(1R,2S,6R,7S,2'S)-5-(2'-hydroxymethyl-pyrrolidin-1'-yl)-endo-tricyclo[5.2.1.0(2,6)]deca-4,8-dien-3-one is described. Knowing the absolute configuration of the prolinol moiety (S) the X-ray diffraction study established the absolute configuration of the title compound. The structure was refined to R-1 = 0.0322 for 1237 reflections (with I greater-than 2 sigma(I)). Crystal data: C15H19NO2, monoclinic, space group P2(1), a = 6.0757(4), b = 11.3473(5), c = 9.5114(7)Angstrom, beta = 104.686(6)degrees, V = 634.32(7) Angstrom(3), and Z = 2.
• Regioselective electrophilic oxidation of a 5-amino- endo -tricyclo[5.2.1.0 2,6 ]decenyl enaminone. Synthesis of a novel heterocyclic compound
  作者：Namakkal G Ramesh、Antonius J.H Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4039(01)01636-7

  日期：2001.10

  An unexpected tandem regioselective oxidation and cyclization of 5-((S)-2'-hydroxymethylpyrrolidin-1'-yl)-endo-tricyclo[5.2.1.0(2,6)]deca-4,8-dien-3-ones 7 is reported. The reaction proceeds smoothly to afford novel tetracyclic compounds 8 and 9 in good yield, The structure of 8 was established by single-crystal X-ray analysis. Surprisingly, the C8-C9 norbornene double bond remains intact under these oxidative conditions. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Asymmetric desymmetrization of pseudo-meso 5-hydroxy-endo-tricyclo[5.2.1.02,6]deca-4,8-dien-3-ones
  作者：Namakkal G Ramesh、Frank J.A.D Bakkeren、Debby de Groot、Umberto Passamonti、Antonius J.H Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4020(01)01007-9

  日期：2001.12

  -tricyclo[5.2.1.02,6]deca-4,8-dien-3-one. Desymmetrization using (S)-prolinol or its methyl ether leads to the corresponding enaminones in high yields and with a de of 50%. Complete separation of the diastereomers has been conveniently achieved via their acetates. The absolute stereochemistry of the major diastereomer was determined by single-crystal X-ray diffraction analysis. Reductive elimination

  从容易获得的伪内消旋-5-羟基-内环-三环[5.2.1.0 2,6 ] deca-4,8-​​dien-3-one开始，已经完成了通往对映体纯的内-三环癸二烯酮系统的新途径。使用（S）-脯氨醇或其甲基醚进行的不对称化以高收率和50％的de产生相应的烯胺酮。非对映异构体的完全分离已通过其乙酸盐方便地实现。主要的非对映异构体的绝对立体化学是通过单晶X射线衍射分析确定的。用氢化锂铝对手性助剂的还原消除以良好的总收率提供了光学纯的母体三环癸二烯酮。