5-cyclohexylamino-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 5-cyclohexylamino-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one
• 英文别名: 5-cyclohexylamino-endo-tricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one；(1S,2R,6S,7R)-5-(cyclohexylamino)tricyclo[5.2.1.02,6]deca-4,8-dien-3-one
• 化学式: C₁₆H₂₁NO
• 分子量: 243.349
• InChiKey: WKNKSSSDZSDVNH-TZCMFKBTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-cyclohexylamino-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-3-one 以 甲醇 为溶剂， 生成 (3aS,4S,7R,7aR)-3-Cyclohexylamino-3a,4,5,6,7,7a-hexahydro-4,7-methano-inden-1-one
  参考文献：
  名称：

  Unusual photochemical behavior of 5-amino-endo-dicyclopentadien-3-ones

  摘要：

  Irradiation of 5-amino-substituted endo-tricyclo[5.2.1.0(2.6)]deca-4,8-dien-3-ones 3 did not lead to the anticipated [pi(2) + pi(2)]-photocyclization to afford bridgehead 1,3-bishomocubyl amines 4. Instead an unexpected photoreduction of the norbornene C(8)-C(9) double bond was observed, which based on D-labelling studies involves a photo-electron transfer process. The desired [pi(2) + pi(2)]-photo-cyclization furnishing 4-amido-substituted 1,3-bishomocubanones 7 could however be effected by N-acylation of the amino function in 3. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02115-7
• 作为产物：
  描述：

  4-环戊烯-1,3-二酮 以 甲苯 为溶剂， 反应 24.0h， 生成 5-cyclohexylamino-endo-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

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 effective regioselective electrophilic halogenation of tricyclo[5.2.1.02,6]decenyl enaminones
  作者：Namakkal G. Ramesh、Erik H. Heijne、Antonius J.H. Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4039(98)00474-2

  日期：1998.5

  4 undergo a surprisingly effective regioselective halogenation using N-halosuccinimides (NXS) under electrophilic conditions. Exclusive α-halogenation is observed using one equiv. of NXS, whereas, either α,γ- or α,N-bishalogenation products are formed in quantitative yields when an additional equiv. of NXS is applied. Most importantly, halogenation of the C8C9 norbornene bond is not observed.

  使用N-卤代琥珀酰亚胺（NXS）在亲电子条件下，对5-氨基-内环-三环[5.2.1.0 2,6 ] deca-4,8-​​dien-3-ones 4进行了令人惊讶的有效区域选择性卤化。使用一个当量可观察到排他性的α-卤代。当额外当量时，α，γ-或α，N-双卤代产物以定量收率形成。NXS的应用。最重要的是，作为C卤化8 C 9降冰片烯键未观察到。
• 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.