cis-3',5'-Diphenyl-1'',3''-dihydrodispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-diol | 229168-07-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-3',5'-Diphenyl-1'',3''-dihydrodispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-diol
• CAS: 229168-07-4
• 化学式: C₂₈H₂₈O₄
• 分子量: 428.528
• InChiKey: FQLAMUJLTXQRNX-YFPWCPNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  32
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  cis-3',5'-Diphenyl-1'',3''-dihydrodispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-diol 在 lithium aluminium tetrahydride 、 磷酸 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 甲苯 为溶剂， 反应 39.0h， 生成 (4bα,7aα,11bβ,15bα)-5,7a,11b,15b-Tetrahydro-4bH-dibenzo[2,3:4,5]pentaleno[1,6-jk]fluorene
  参考文献：
  名称：

  Benzoannelatedcis,cis,cis,trans-[5.5.5.6]Fenestranes: Syntheses, Base Lability, and Flattened Molecular Structure of Strained Epimers of the all-cis Series

  摘要：

  Tribenzofenestranes possessing the strained cis,cis,cis.trans[5.5.5.6]-fenestrane skeleton have been synthesized from cis-2.6-diphenylspiro[cyclohexane-1.2 ' -indane]-1 ' .3 ' -diols by twofold cyclodehydration, in striking analogy to the strategy used previously to construct the stereoisomeric all-cis-tribenzo[5.5.5.6]fenestranes from the corresponding trans-diphenylspirodiols. In this manner, both of the parent hydrocarbons, all-cis-tribenzo[5.5.5.6]fenestrane 3 and cis.cis.cis.trans-tribenzo[5.5.5.6]fenestrane 4, have been made accessible from the spirodiketones 5 and 6, respectively. The C6-functionalized derivatives of 4-cis.cis.cis.trans-fenestranol 9 and cis.cis.cis.trans-fenestranone 12-were prepared through cis-diphenylspirotriol 8 and cis-diphenyldispiroacetaldiol 11. by using the same strategy. The cis,cis, cis.trans-[5.5.5.6]fenestrane framework readily epimerizes to the more stable all-cis isomers under basic conditions, but is stable under neutral or acidic conditions. For example, cis,cis.cis.trans-fenestranone 12 yielded all-cis fenestrane 3 under Wolff-Kishner conditions, but cis,cis,cis,trans-isomer 4 under Clemmensen conditions. Epimerization was also circumvented by radical-induced desulfurization of fenestrane dithiolane 15 with nBu(3)SnH/AIBN. producing 4 in excellent yields. A single-crystal X-ray structure analysis of 4 revealed that, in accordance with force field and semi-empirical MO calculations. the extra strain of the benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestratriene framework [E-strain(4)- E-strain(3) = 46 kJ mol(-1)] is due both to the almost perfect boat conformation of the six-membered ring and to considerable bond angle widening at the central non-bridged C4b-Cl5d-C11b unit (121). H/D exchange experiments with the cis cis,cis,trans hydrocarbon 4 under basic conditions demonstrated that the strain-induced epimerization to 3 occurs through direct deprotonation of the "epimeric" benzylic bridgehead C7a-H bond, which was found to be more acidic than the two C-H bonds at the benzhydrylic bridgeheads.

  DOI：

  10.1002/1521-3765(20010803)7:15<3387::aid-chem3387>3.0.co;2-6
• 作为产物：
  描述：

  (2R,6S)-2,6-diphenylspiro[cyclohexane-1,2′-indene]-1′,3′,4-trione 在 lithium aluminium tetrahydride 、 4 A molecular sieve 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 cis-3',5'-Diphenyl-1'',3''-dihydrodispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-diol
  参考文献：
  名称：

  Benzoannelatedcis,cis,cis,trans-[5.5.5.6]Fenestranes: Syntheses, Base Lability, and Flattened Molecular Structure of Strained Epimers of the all-cis Series

  摘要：

  Tribenzofenestranes possessing the strained cis,cis,cis.trans[5.5.5.6]-fenestrane skeleton have been synthesized from cis-2.6-diphenylspiro[cyclohexane-1.2 ' -indane]-1 ' .3 ' -diols by twofold cyclodehydration, in striking analogy to the strategy used previously to construct the stereoisomeric all-cis-tribenzo[5.5.5.6]fenestranes from the corresponding trans-diphenylspirodiols. In this manner, both of the parent hydrocarbons, all-cis-tribenzo[5.5.5.6]fenestrane 3 and cis.cis.cis.trans-tribenzo[5.5.5.6]fenestrane 4, have been made accessible from the spirodiketones 5 and 6, respectively. The C6-functionalized derivatives of 4-cis.cis.cis.trans-fenestranol 9 and cis.cis.cis.trans-fenestranone 12-were prepared through cis-diphenylspirotriol 8 and cis-diphenyldispiroacetaldiol 11. by using the same strategy. The cis,cis, cis.trans-[5.5.5.6]fenestrane framework readily epimerizes to the more stable all-cis isomers under basic conditions, but is stable under neutral or acidic conditions. For example, cis,cis.cis.trans-fenestranone 12 yielded all-cis fenestrane 3 under Wolff-Kishner conditions, but cis,cis,cis,trans-isomer 4 under Clemmensen conditions. Epimerization was also circumvented by radical-induced desulfurization of fenestrane dithiolane 15 with nBu(3)SnH/AIBN. producing 4 in excellent yields. A single-crystal X-ray structure analysis of 4 revealed that, in accordance with force field and semi-empirical MO calculations. the extra strain of the benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestratriene framework [E-strain(4)- E-strain(3) = 46 kJ mol(-1)] is due both to the almost perfect boat conformation of the six-membered ring and to considerable bond angle widening at the central non-bridged C4b-Cl5d-C11b unit (121). H/D exchange experiments with the cis cis,cis,trans hydrocarbon 4 under basic conditions demonstrated that the strain-induced epimerization to 3 occurs through direct deprotonation of the "epimeric" benzylic bridgehead C7a-H bond, which was found to be more acidic than the two C-H bonds at the benzhydrylic bridgeheads.

  DOI：

  10.1002/1521-3765(20010803)7:15<3387::aid-chem3387>3.0.co;2-6

文献信息

• Synthesis and base-induced epimerization of cis,cis,cis,trans-tribenzo[5.5.5.6]fenestranes
  作者：Björn Bredenkötter、Dieter Barth、Dietmar Kuck、Dietmar Kuck

  DOI：10.1039/a902024a

  日期：——

  Strained cis,cis,cis,trans-tribenzo[5.5.5.6]fenestranes are accessible in good yield by two-fold cyclodehydration of cis-2,6-diphenylspiro[cyclohexane-1,2′-indane]-1′,3′-diols and the particularly high acidity of their ‘inverted’ benzylic bridgehead C–H bonds, causing facile epimerization to the more stable all-cis-tribenzo[5.5.5.6]fenestranes, is shown.

  拉紧的顺、顺、顺、反-三苯并[5.5.5.6]窗烃可以通过对顺-2,6-二苯基螺[环己烷-1,2′-印度]-1′,3′-二醇进行两次环脱水反应，获得良好的产率。其“倒转”的苯基桥头C-H键的特别高酸度使得在这里易于表异构化形成更稳定的全顺-三苯并[5.5.5.6]窗烃。