[(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde | 251319-31-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde
• 英文别名: [(1R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde；(1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene)acetaldehyde；(2-bornylidene)acetaldehyde
• CAS: 251319-31-0
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: OCIAJRRPMMEPOE-IMQVEDSNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.96
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde 在 manganese(IV) oxide 、 正丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 3-tosyl-4-phenyl-1-(1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene)but-3-en-2-one
  参考文献：
  名称：

  二乙烯基酮由路易斯酸和碱介导的化学选择性环化成环己烯酮。

  摘要：

  [反应：见正文]在温和的反应条件下，已经完成了由空间需求的路易斯酸和胺碱介导的二乙烯基酮向环己烯酮的化学选择性环化反应。还证明了该方法对八元环合成的扩展。

  DOI：

  10.1021/ol048545b
• 作为产物：
  描述：

  (1R,2S,4R)-2-ethynyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol 在 甲酸 作用下， 反应 2.0h， 生成 [(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde
  参考文献：
  名称：

  Synthesis of chiral benzacridone derivatives by three-component condensation

  摘要：

  A three-component condensation of (2-bornylidene)acetaldehyde and 2-naphthylamine with various, in particular, dissymmetrical, cyclic beta-diketones afforded derivatives of 12-(2-bornylidene)methyl-8,9,10,12-tetrahydro-7H-benzo[a]acridin-11-one containing in the structure three and more asymmetrical carbon atoms. Steric factors govern the prevailing formation of (12R)-isomers of benzacridones (R/SH a parts per thousand 7: 5) and the orientation of the substituents of the cyclohexenone fragment. These factors ensure also the regiospecificity of the reaction leading exclusively to the formation of 8,9-disubstituted benzacridones at the use of 4,5-disubstituted cyclohexane-1,3-diones.

  DOI：

  10.1134/s1070428009020067

文献信息

• Preparation of Chiral Hydroxy Carbonyl Compounds and Diols by Ozonolysis of Olefinic Isoborneol and Fenchol Derivatives: Characterization of Stable Ozonides by1H-,13C-, and17O-NMR and Electrospray Ionization Mass Spectrometry
  作者：Kalina Kostova、Vladimir Dimitrov、Svetlana Simova、Manfred Hesse

  DOI：10.1002/(sici)1522-2675(19990908)82:9<1385::aid-hlca1385>3.0.co;2-y

  日期：1999.9.8

  The allylic and homoallylic alcohols 1-8, prepared from (+)-camphor and (-)-fenchone, were ozonized in Et2O at -78 and treated with Et3N or LiAlH4 to give the chiral hydroxy carbonyl compounds 9-16 and the diols 17-24, respectively (Scheme I). In the case of the diols 19 and WI the formation of new chiral centers proceeded with high diastereoselectivity. These diols were prepared highly diastereoselectively also by LiAlH4 reduction of the hydroxy carbonyl compounds 11 and 16a, respectively (Scheme 2). The absolute configuration of the new chiral centers in 19 and 24 was determined by X-ray and NMR methods. The ozonization of compounds 2, 3, 7, and 8 provided the relatively stable hydroxy-substituted 1,2,4-trioxolane derivatives (ozonides) 37-40 (Scheme 5) which were characterized by H-1- and C-13-NMR spectra. ESI-MS, and natural-abundance O-17-NMR spectra.
• Synthesis of chiral benzoacridinone derivatives by three-component condensation of [(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde with naphthalen-1-amine and cyclic β-diketones
  作者：S. S. Koval’skaya、N. G. Kozlov、E. A. Dikusar

  DOI：10.1134/s1070428010080038

  日期：2010.8

  Three-component condensation of [(1S,4S)-1,7,7-trimethylbicyclo[2.2.1] hept-2-ylidene] acetaldehyde with naphthalen-1-amine and cyclic beta-diketones gave 7-[(1S,4S)-1,7,7-trimethylbicyclo[2.2.1] hept-2-ylidenemethyl]-7,8,9,10,11,12-hexahydro-7H-benzo[c] acridin-8-one derivatives possessing three or more asymmetric carbon atoms. Steric factors were found to be responsible for the predominant formation of the (7R)-isomers (R/S approximate to 7 : 5) and orientation of substituents in the cyclohexenone fragment. The same factors determined complete regioselectivity of the reaction with methyl 2,4-dioxocyclohexane-1-carboxylates as dicarbonyl component, which led to exclusive formation of methyl 8-oxobenzoacridine-11-carboxylates. In the reaction of [(1S, 4S)-1,7,7-trimethylbicyclo[2.2.1] hept-2-ylidene] acetaldehyde with naphthalen-1-amine and barbituric acid as dicarbonyl component, the only product was that formed by two-component condensation of barbituric acid with bicyclic aldehyde.
• Chemoselective Cyclizations of Divinyl Ketones to Cyclohexenones Mediated by Lewis Acid and Base
  作者：Nabi A. Magomedov、Piero L. Ruggiero、Yuchen Tang

  DOI：10.1021/ol048545b

  日期：2004.9.1

  [reaction: see text] Chemoselective cyclizations of divinyl ketones to cyclohexenones mediated by a sterically demanding Lewis acid and an amine base have been accomplished under mild reaction conditions. The extension of this methodology to the synthesis of eight-membered rings is also demonstrated.

  [反应：见正文]在温和的反应条件下，已经完成了由空间需求的路易斯酸和胺碱介导的二乙烯基酮向环己烯酮的化学选择性环化反应。还证明了该方法对八元环合成的扩展。
• Synthesis of chiral benzacridone derivatives by three-component condensation
  作者：S. S. Koval’skaya、N. G. Kozlov、E. A. Dikusar

  DOI：10.1134/s1070428009020067

  日期：2009.2

  A three-component condensation of (2-bornylidene)acetaldehyde and 2-naphthylamine with various, in particular, dissymmetrical, cyclic beta-diketones afforded derivatives of 12-(2-bornylidene)methyl-8,9,10,12-tetrahydro-7H-benzo[a]acridin-11-one containing in the structure three and more asymmetrical carbon atoms. Steric factors govern the prevailing formation of (12R)-isomers of benzacridones (R/SH a parts per thousand 7: 5) and the orientation of the substituents of the cyclohexenone fragment. These factors ensure also the regiospecificity of the reaction leading exclusively to the formation of 8,9-disubstituted benzacridones at the use of 4,5-disubstituted cyclohexane-1,3-diones.