cis-2,6-Diphenylspiro[cyclohexane-1,2'-[2H]indene]-1',3'-diol | 229168-03-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-2,6-Diphenylspiro[cyclohexane-1,2'-[2H]indene]-1',3'-diol
• 英文别名: (2'R,6'S)-2',6'-diphenylspiro[1,3-dihydroindene-2,1'-cyclohexane]-1,3-diol
• CAS: 229168-03-0
• 化学式: C₂₆H₂₆O₂
• 分子量: 370.491
• InChiKey: DEBANWAYFZFBSB-UPCUUYMMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-2,6-Diphenylspiro[cyclohexane-1,2'-[2H]indene]-1',3'-diol 在 氘代二甲亚砜 、 磷酸 、 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 反应 39.0h， 生成 (4bα,7aβ,11bα,15bβ)-7a,11b,15b-Trideutero-5,6,7,7a,11b,15b-hexahydro-4bH-dibenzo[2,3:4,5]pentaleno[1,6-jk]fluorene
  参考文献：
  名称：

  Synthesis and base-induced epimerization of cis,cis,cis,trans-tribenzo[5.5.5.6]fenestranes

  摘要：

  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。

  DOI：

  10.1039/a902024a
• 作为产物：
  描述：

  (2β,6α)-2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione 在 lithium aluminium tetrahydride 、 儿萘酚硼烷 作用下， 以 四氢呋喃 、 乙醇 、 氯仿 为溶剂， 反应 37.0h， 生成 cis-2,6-Diphenylspiro[cyclohexane-1,2'-[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