(1S,4S,5S,8S,9S,12S)-4,7,8,9,11,12-hexahydro-1,4:5,8:9,12-trimethanotriphenylene-2,6,10(1H,3H,5H)-trione | 1040140-89-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (1S,4S,5S,8S,9S,12S)-4,7,8,9,11,12-hexahydro-1,4:5,8:9,12-trimethanotriphenylene-2,6,10(1H,3H,5H)-trione
• 英文别名: (-)-syn-trisoxonorbornabenzene；(1S,4S,7S,10S,13S,16S)-heptacyclo[14.2.1.14,7.110,13.02,15.03,8.09,14]henicosa-2,8,14-triene-5,11,17-trione
• CAS: 1040140-89-3
• 化学式: C₂₁H₁₈O₃
• 分子量: 318.372
• InChiKey: JNWLMUGGXSLVNB-PYZHKEBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,4S,5S,8S,9S,12S)-4,7,8,9,11,12-hexahydro-1,4:5,8:9,12-trimethanotriphenylene-2,6,10(1H,3H,5H)-trione 在 六甲基磷酰三胺 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以75%的产率得到[(1S,4S,7S,10S,13S,16S)-11,17-bis(trifluoromethylsulfonyloxy)-5-heptacyclo[14.2.1.14,7.110,13.02,15.03,8.09,14]henicosa-2,5,8,11,14,17-hexaenyl] trifluoromethanesulfonate
  参考文献：
  名称：

  对映体纯的碘降冰片烯的区域选择性环三聚制备C3对称的手性顺式Trisnorborna苯。

  摘要：

  通过钯纳米团簇催化对映纯的碘化冰片的新的区域选择性环三聚，合成了具有刚性杯形结构的C 3-对称同手性（-）-顺式-trisoxonorborna苯1。环三聚的产率取决于钯簇的稳定性，其由反应混合物的外观和TEM图像确定。包括新开发的环三聚反应在内的短步伐就建立了（-）- syn - 1的高效制备方法。如此制备的同手性（-）- syn - 1可以用作合成C 3的关键中间体具有螺旋形取代基的对称对称手性杯状分子。通过钯催化的与（-）- syn - 1的相应磷酸酯和三氟甲磺酸酯的偶合钯偶联反应已很好地证明了几种取代基的引入。

  DOI：

  10.1002/asia.200900132
• 作为产物：
  描述：

  (1S,4S)-5-oxobicyclo[2.2.1]hept-2-en-2-yl diphenyl phosphate 在 三氟甲磺酸 、 三氟甲磺酸三甲基硅酯 、 sodium iodide 、 四丁基醋酸铵 、 palladium diacetate 、 sodium carbonate 、 三苯基膦 作用下， 以 乙腈 、 1,4-二氧六环 为溶剂， 反应 3.5h， 以28%的产率得到(1S,4S,5S,8S,9S,12S)-4,7,8,9,11,12-hexahydro-1,4:5,8:9,12-trimethanotriphenylene-2,6,10(1H,3H,5H)-trione
  参考文献：
  名称：

  Asymmetric Synthesis of a Chiral Buckybowl, Trimethylsumanene

  摘要：

  The first asymmetric synthesis of a chiral buckybowl, a C(3) symmetric (C)-8,13,18-trimethylsumanene (1), was achieved by employing a synthetic strategy that translates chirality at sp(3) centers into bowl chirality. The synthesis features a syn selective cyclotrimerization of an enantiopure halonorbornene derivative, tandem ring-opening/closing olefin metathesis reactions, and DDQ oxidation at low temperature. The bowl-to-bowl inversion energy of 1 was determined as 21.6 kcal/mol by circular dichroism spectra measurement.

  DOI：

  10.1021/ja802822k

文献信息

• Trimethylsumanene: Enantioselective Synthesis, Substituent Effect on Bowl Structure, Inversion Energy, and Electron Conductivity
  作者：Shuhei Higashibayashi、Ryoji Tsuruoka、Yarasi Soujanya、Uppula Purushotham、G. Narahari Sastry、Shu Seki、Takeharu Ishikawa、Shinji Toyota、Hidehiro Sakurai

  DOI：10.1246/bcsj.20110286

  日期：2012.4.15

  C3 symmetric chiral trimethylsumanene was enantioselectively synthesized through Pd-catalyzed syn-selective cyclotrimerization of an enantiomerically pure iodonorbornenone, ring-opening/closing olefin metathesis, and oxidative aromatization where the sp3 stereogenic center was transmitted to the bowl chirality. Chiral HPLC analysis/resolution of the derivatives were also achieved. Based on theoretical calculations, the columnar crystal packing structure of sumanene and trimethylsumanene was interpreted as due to attractive electrostatic or CH–π interaction. According to the experimental and theoretical studies, the bowl depth and inversion energy were found to increase on methylation for sumanene in contrast to corannulene. Dissimilarities of the effect of methylation on the bowl structure and inversion energy of sumanene and corannulene were ascribed to differences in steric repulsion. A double-well potential model was fitted to the bowl structure–inversion energy correlation of substituted sumanenes, with a small deviation. The effects of various substituents on the sumanene structure and bowl-inversion energy were analyzed by density functional theory calculations, and it was shown that the bowl rigidity is controlled by a combination of electronic and steric effects of the substituents. The electron conductivity of trimethylsumanene was investigated by time-resolved microwave conductivity method, compared with that of sumanene.

  通过钯催化对映体纯碘降冰片烯酮的同步选择性环三聚反应、开环/闭环烯烃偏聚反应和氧化芳香化反应（其中 sp3 立体中心传递到碗手性），对映体选择性地合成了 C3 对称手性三甲基马来烯。此外，还实现了衍生物的手性 HPLC 分析/分辨。根据理论计算，苏木烯和三甲基苏木烯的柱状晶包装结构被解释为吸引力静电或 CH-π 相互作用所致。根据实验和理论研究发现，与茱萸烯相比，苏曼烯甲基化时的碗状深度和反转能都会增加。甲基化对苏木烯和芫荽烯的碗状结构和反转能的不同影响被归因于立体斥力的差异。双阱势能模型与取代苏木烯的碗状结构-反转能相关性相拟合，但偏差较小。通过密度泛函理论计算分析了各种取代基对苏曼烯结构和碗状反转能的影响，结果表明碗状刚性是由取代基的电子效应和立体效应共同控制的。采用时间分辨微波传导法研究了三甲基苏马烯的电子传导性，并与苏马烯的电子传导性进行了比较。
• Stereoselective Cyclotrimerization of Enantiopure Iodonorbornenes Catalyzed by Pd Nanoclusters for <i>C</i>₃ or <i>C</i>_3<i>v</i> Symmetric <i>syn</i>-Tris(norborneno)benzenes
  作者：Shuhei Higashibayashi、A. F. G. Masud Reza、Hidehiro Sakurai

  DOI：10.1021/jo100710h

  日期：2010.7.2

  C3 or C3v symmetric enantiopure syn-tris(norborneno)benzenes with various functional groups were synthesized through Pd-catalyzed cyclotrimerization of enantiopure iodonorbornenes. The generality of Pd-catalyzed cyclotrimerization for syn-tris(norborneno)benzenes were well-demonstrated.

  通过Pd对映体纯的碘基降冰片烯的环三聚反应，合成了具有各种官能团的C 3或C 3 v对称的对映体纯的顺式三（降冰片烯）苯。Pd催化合成的三（norborneno）苯的环三聚反应的普遍性已得到充分证明。
• Chiral phenylazomethine cage
  作者：Ryo Shomura、Shuhei Higashibayashi、Hidehiro Sakurai、Yoshitaka Matsushita、Akira Sato、Masayoshi Higuchi

  DOI：10.1016/j.tetlet.2011.11.141

  日期：2012.2

  Enantiopure phenylazomethine cages ((S)- and (R)-PAC) were tion of chiral (5)- and (R)-syn-tris(norborneno)benzene with (56% and 50%), respectively. The structure and chirality of PACs by NMR, CD, X-ray diffraction and DFT calculations. selectively obtained by one-pot dehydrap-phenylenediamine in moderate yields in solution and solid state were confirmed by NMR, CD, X-ray diffraction and DFT calculations. (C) 2011 Elsevier Ltd. All rights reserved.
• Asymmetric Synthesis of a Chiral Buckybowl, Trimethylsumanene
  作者：Shuhei Higashibayashi、Hidehiro Sakurai

  DOI：10.1021/ja802822k

  日期：2008.7.1

  The first asymmetric synthesis of a chiral buckybowl, a C(3) symmetric (C)-8,13,18-trimethylsumanene (1), was achieved by employing a synthetic strategy that translates chirality at sp(3) centers into bowl chirality. The synthesis features a syn selective cyclotrimerization of an enantiopure halonorbornene derivative, tandem ring-opening/closing olefin metathesis reactions, and DDQ oxidation at low temperature. The bowl-to-bowl inversion energy of 1 was determined as 21.6 kcal/mol by circular dichroism spectra measurement.
• Preparation of<i>C</i>₃-Symmetric Homochiral<i>syn</i>-Trisnorbornabenzenes through Regioselective Cyclotrimerization of Enantiopure Iodonorbornenes
  作者：A. F. G. Masud Reza、Shuhei Higashibayashi、Hidehiro Sakurai

  DOI：10.1002/asia.200900132

  日期：2009.8.3

  mixtures. The efficient preparation of (−)‐syn‐1 was established in short steps, including the newly developed cyclotrimerization reaction. The thus‐prepared homochiral (−)‐syn‐1 can serve as a key intermediate for the synthesis of C3‐symmetric homochiral cup‐shaped molecules with a helical arrangement of substituents. Introduction of several types of substituents was well demonstrated through palladium‐catalyzed

  通过钯纳米团簇催化对映纯的碘化冰片的新的区域选择性环三聚，合成了具有刚性杯形结构的C 3-对称同手性（-）-顺式-trisoxonorborna苯1。环三聚的产率取决于钯簇的稳定性，其由反应混合物的外观和TEM图像确定。包括新开发的环三聚反应在内的短步伐就建立了（-）- syn - 1的高效制备方法。如此制备的同手性（-）- syn - 1可以用作合成C 3的关键中间体具有螺旋形取代基的对称对称手性杯状分子。通过钯催化的与（-）- syn - 1的相应磷酸酯和三氟甲磺酸酯的偶合钯偶联反应已很好地证明了几种取代基的引入。