(4aRS,9aRS)-1,2,3,4,4a,9a-hexahydro-4a-methylfluorene | 120360-71-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (4aRS,9aRS)-1,2,3,4,4a,9a-hexahydro-4a-methylfluorene
• 英文别名: cis-1,2,3,4,4a,9a-hexahydro-4a-methylfluorene；cis-4a-methyl-1,2,3,4,4a,9a-hexahydrofluorene；(4aR,9aR)-4a-methyl-1,2,3,4,9,9a-hexahydrofluorene
• CAS: 120360-71-6
• 化学式: C₁₄H₁₈
• 分子量: 186.297
• InChiKey: INIHVELBWZNMFX-TZMCWYRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  2-(o-Bromobenzyl)-1-methylenecyclohexane 在 palladium diacetate 、 sodium formate 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以77%的产率得到(4aRS,9aRS)-1,2,3,4,4a,9a-hexahydro-4a-methylfluorene
  参考文献：
  名称：

  An Efficient Palladium Catalyzed Stereocontrolled Synthesis of 4a-Angular Methyl Substituted Hydrofluorenes

  摘要：

  A high yield s tereoselective synthesis of 4a-angularly methyl substituted cis-hexahydrofluorenes 5a-h and tetrahydrofluorenes 7a,b has been developed by palladium-catalyzed intramolecular Heck-type cyclization of the respective exo-olefins 4a-h and 4a,b through exclusive 5-exo-trig mode.

  DOI：

  10.1080/00397919508015849

文献信息

• Regiochemistry in Aryl Radical Cyclization onto Methylenecycloalkanes
  作者：Hiroyuki Ishibashi、Tetsuya Kobayashi、Sayaka Nakashima、Osamu Tamura

  DOI：10.1021/jo001086h

  日期：2000.12.1

  Bu(3)SnH-mediated aryl radical cyclization onto methylenecycloalkanes having a phenylthio, an ester, or a nitrile group at the terminus of the alkenic bond provides exclusively exo cyclization products. The results are in sharp contrast to those reported for nonsubstituted methylenecycloalkanes, which give exclusively endo cyclization products. Formation of endo cyclization products has been suggested

  Bu（3）SnH介导的芳基自由基环化成在烯键末端具有苯硫基，酯或腈基的亚甲基环烷烃，仅提供外环化产物。结果与未取代的亚甲基环烷烃报告的结果形成鲜明对比，后者仅产生内环化产物。内环化产物的形成已被认为是芳基连续5-外向环化和新叶重排的结果。选择性外芳基自由基环化提供了一种合成含苄基季碳原子的稠合芳族化合物的新方法。
• Reactions of benzyl carbinols with fluorosulfuric acid
  作者：Colin J. Barrow、Steven T. Bright、James M. Coxon、Peter J. Steel

  DOI：10.1021/jo00272a016

  日期：1989.5
• Cyclization of Aryllithiums Tethered to Methylenecycloalkanes:  Stereoselective Synthesis of 4<i>a</i>-Substituted <i>cis</i>-Hexahydrofluorenes
  作者：William F. Bailey、Tahir Daskapan、Sriram Rampalli

  DOI：10.1021/jo020593r

  日期：2003.2.1

  The cyclization of an aryllithium tethered to a methylenecycloalkane, generated from 2-(o-bromobenzyl)-1-methylenecycloalkanes 1, 2, and 3 by low-temperature lithium-bromine exchange, has been found to be a kinetically slow but thermodynamically favorable process that proceeds at a convenient rate in an exclusively 5-exo fashion when solutions of the aryllithium in n-heptane-di-n-butyl ether (9:1 v/v) are warmed to 45 degreesC. The cyclization affords stereoisomerically pure cis-fused products (7 and 8) when the methylenecycloalkane is five- or six-membered but it is less stereoselective when the methylenecycloalkane is seven-membered. The ring-closure of the aryllithium derived from 2-(o-bromobenzyl)-1-methylenecyclohexane (2) provides an experimentally convenient route to stereoisomerically pure 4a-substituted cis-hexahydrofluorenes in 60-90% isolated yield.
• Sulfur-Controlled <i>Exo</i> Selective Aryl Radical Cyclization onto <i>Exo</i>-Methylenecycloalkanes
  作者：Hiroyuki Ishibashi、Tetsuya Kobayashi、Daisuke Takamasu

  DOI：10.1055/s-1999-2826

  日期：1999.8
• BARROW, COLIN J.;BRIGHT, STEVEN T.;COXON, JAMES M.;STEEL, PETER J., J. ORG. CHEM., 54,(1989) N1, C. 2542-2549
  作者：BARROW, COLIN J.、BRIGHT, STEVEN T.、COXON, JAMES M.、STEEL, PETER J.

  DOI：——

  日期：——