cis-3',5'-Diphenyldispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-dione | 375369-51-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: cis-3',5'-Diphenyldispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-dione
• CAS: 375369-51-0
• 化学式: C₂₈H₂₄O₄
• 分子量: 424.496
• InChiKey: DKFLMNQELAAWPU-PSWAGMNNSA-N

反应信息

• 作为反应物：
  描述：

  cis-3',5'-Diphenyldispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-dione 在 镍 lithium aluminium tetrahydride 、 磷酸 、 三氟化硼乙醚 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 溶剂黄146 、 二甲基亚砜 、 甲苯 为溶剂， 反应 51.0h， 生成 (4bα,7aβ,11bα,15bβ)-5,6,7,7a,11b,15b-Hexahydro-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：

  乙二醇 、 (2R,6S)-2,6-diphenylspiro[cyclohexane-1,2′-indene]-1′,3′,4-trione 在 4 A molecular sieve 、 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以99%的产率得到cis-3',5'-Diphenyldispiro[1,3-dioxolane-2,1'-cyclohexane-4',2''-[2H]indene]-1'',3''-dione
  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