cis-transoid-cis-tricyclo[6.3.0.0^2,6]undecane | 120052-74-6

• 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: cis-transoid-cis-tricyclo[6.3.0.0^2,6]undecane
• 英文别名: (3aR,3bR,6aR,7aR)-2,3,3a,3b,4,5,6,6a,7,7a-decahydro-1H-cyclopenta[a]pentalene
• CAS: 120052-74-6
• 化学式: C₁₁H₁₈
• 分子量: 150.264
• InChiKey: ZJLJFSYHUDYXIE-GWOFURMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1,6-己二醇 在 palladium on activated charcoal molecular sieve 、 Celite 、 氢气 、 potassium carbonate 、 二乙胺 、 pyridinium chlorochromate 、 甲胺 作用下， 以 正己烷 、 二氯甲烷 、 苯 为溶剂， 反应 24.0h， 生成 cis-transoid-cis-tricyclo[6.3.0.0^2,6]undecane
  参考文献：
  名称：

  Construction of linear-fused tricyclopentanoids by intramolecular [6 + 2] cycloadditions of fulvenes with enamines

  摘要：

  DOI：

  10.1021/ja00304a065

文献信息

• Synthesis of<i>cis-transoid-cis-</i>and<i>cis-cisoid-cis-</i>Tricyclo[6.3.0.0^2,6]undecan-1-ols
  作者：Kiyomi Kakiuchi、Hideyuki Takeuchi、Yoshito Tobe、Yoshinobu Odaira

  DOI：10.1246/bcsj.58.1613

  日期：1985.5

  Two isomeric linear triquinanes, cis-transoid-cis- and cis-cisoid-cis-tricyclo[6.3.0.02,6]undecan-1-ols, were effectively synthesized by means of the modified Barbier cyclization.

  通过改良的巴比尔环化反应，两种同分异构的线性三羟基环己烷（顺-反-顺-和顺-顺-反-顺-三环[6.3.0.02,6]十一烷-1-醇）被有效地合成出来。
• Stereochemical control of transannular radical cyclizations. A new approach to the synthesis of linearly fused cyclopentanoids
  作者：Jeffrey D. Winkler、V. Sridar

  DOI：10.1021/ja00267a061

  日期：1986.4

  Construction d'un cyclopenta [a] pentalene carboxylate-3 d'ethyle precurseur de la corioline

  Construction d'un cyclopenta [a] pentalene carboxylate-3 d'ethyle precurseur de la corioline
• Reductive Rearrangement with Hydride Transfer of Linearly and Angularly Fused Triquinanes
  作者：Kiyomi Kakiuchi、Masaki Ue、Shuichi Kumanoya、Hideyuki Takeuchi、Yoshito Tobe、Yoshinobu Odaira

  DOI：10.1246/cl.1986.1479

  日期：1986.9.5

  Relationship between linearly and angularly fused triquinanes is elucidated by reductive rearrangements with hydride transfer of tricyclo[6.3.0.02,6]undecan-1-ol, tricyclo[6.3.0.01,5]undecan-6-ols, and tricyclo[5.3.1.01,5]undecan-11-ol.

  通过三环[6.3.0.02,6]十一烷-1-醇、三环[6.3.0.01,5]十一烷-6-醇和三环[5.3.1.01,5]十一烷-11-醇的氢化物转移还原重排，阐明了线型融合三喹啉和角型融合三喹啉之间的关系。
• Electroorganic chemistry. 140. Electroreductively promoted intra- and intermolecular couplings of ketones with nitriles.
  作者：Tatsuya Shono、Naoki Kise、Taku Fujimoto、Naoto Tominaga、Hiroshi Morita

  DOI：10.1021/jo00052a036

  日期：1992.12

  Electroreduction of gamma and delta-cyano ketones in i-PrOH with Sn cathode gave alpha-hydroxy ketones and their dehydroxylated ketones as the intramolecularly coupled products. Guaiazulene, (-)-valeranone, polyquinanes, dihydrojasmone, methyl dihydrojasmonate, and rosaprostol have been synthesized by utilizing this electroreductive intramolecular coupling of gamma and delta-cyano ketones in one of the key steps. Similarly, electroreduction of a mixture of ketone and nitrile gave the corresponding intermolecularly coupled product. The product obtained by the electroreductive intermolecular coupling of (+)-dihydrocarvone with acetonitrile has been found to be the precursor of an effective chiral ligand for the enantioselective addition of diethylzinc to aldehydes.
• Generation of [5.5.<i>n</i>] Tricyclic Ring Systems by Radical-Promoted Inter- and Intramolecular [3 + 2] Cycloadditions
  作者：Michael E. Jung、Heather L. Rayle

  DOI：10.1021/jo9706133

  日期：1997.7.1

  A new method for the synthesis of[5.5.n] tricyclic ring systems via radical fragmentation and double cyclization is described. The general process (Scheme 1) involves addition of an alkylthio radical to an alkenylcyclopropane 1 to generate the cyclopropylcarbinyl radical which opens to the homoallylic radical; this radical then adds to an alkene or alkyne radical trap to give a new alkyl radical which then adds back to the thioalkyl allylic system to generate, after loss of the alkylthio radical, the bi- or tricyclic product, 2, thus making the process analogous to a [3 + 2] cycloaddition. Thus addition of the butylthio radical (generated by photolysis of dibutyl disulfide) to the bicyclo-[3.1.0]hex-2-en-6-yl carboxylate 3 in the presence of an alkene or alkyne-either an acyclic radical trap, e.g., ethyl vinyl ether, isopropenyl acetate, methyl acrylate, or methyl propiolate, or a cyclic one, e.g., cyclopentenone, dihydrofuran, cyclopentenyl acetate, or cyclopentene-affords the desired bi- or tricyclic products 9-16 in yields of 54-88%. One can also use 6-vinylbicyclo[3.1.0]hexan-2-one (4) as the alkenylcyclopropane unit. Trapping of the radical generated by addition of butylthio radical to 4 with ethyl vinyl ether or cyclopentene affords the bi- and tricyclic products 17 and 18 in 66-68% yields. The products are formed as diastereomeric mixtures in all cases. This cyclization process can also be carried out in an intramolecular fashion, e.g., isomerization of the ketones 25 and 27 or the esters 28-30 with butylthio radical to give the tricyclic products 31-35 and 41-43. The use of dimethyl-substituted alkenes gives reasonably good diastereoselectivity favoring the cis-syn-cis isomer over the cis-anti-cis isomer, e.g., 7.5:1 for 33 over 34 and 4.2:1 for 41 over 42. The structures of the diastereomeric products were proven by comparison of the NMR spectra of the saturated analogues, which are known for the unsubstituted series and differ in their symmetry properties for the dimethyl-substituted case. These results indicate that the cyclization of a stabilized 5-hexenyl radical, e.g., 45 in Scheme 8, is reversible and leads to the most stable final product.