(2β,6α)-2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (2β,6α)-2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione
• 英文别名: (3R,5R)-3,5-diphenylspiro[cyclohexane-4,2'-indene]-1,1',3'-trione
• 化学式: C₂₆H₂₀O₃
• 分子量: 380.443
• InChiKey: JCRKSTFTQQLWFT-DHIUTWEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  29
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2β,6α)-2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione 在 sodium cyanoborohydride 、 对甲苯磺酸 、 对甲苯磺酰肼 作用下， 以 环丁砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 以32%的产率得到trans-2,6-Diphenylspiro[cyclohexane-1,2'-[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
• 作为产物：
  描述：

  苄叉丙酮 、 2-(苯基亚甲基)茚-1,3-二酮 在 邻硝基苯甲酸 、 (8R,9R)-9-amino(9-desoxy)-epi-cinchonine 作用下， 以 二氯甲烷 为溶剂， 反应 120.0h， 以73%的产率得到(2β,6α)-2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione
  参考文献：
  名称：

  扩大伯胺催化的范围：茚满二酮融合的2,6-二取代的反式-螺环己酮的立体选择性合成

  摘要：

  证实了金鸡纳生物碱衍生的手性伯胺催化的对映选择性方法，该方法用于合成热力学上较不稳定的茚满的二氮杂茚并稠合的2，6-反式-二取代的螺环己酮。反式异构体的两种对映体形式均以优异的收率和对映选择性获得。此外，在环己酮环上带有一个额外的α-取代基的对映体反式螺环烷被差向异构化成其热力学稳定的顺式对应物，几乎没有对映选择性损失，证明了这种转化的可行性。机理研究揭示了形成相应产物的两个竞争途径，一致的狄尔斯-阿尔德反应和逐步的迈克尔加成。

  DOI：

  10.1021/acs.joc.5b02921

文献信息

• The First Organocatalytic Hetero-Domino Knoevenagel-Diels-Alder-Epimerization Reactions: Diastereoselective Synthesis of Highly Substituted Spiro[cyclohexane-1,2′-indan]-1′,3′,4-triones
  作者：Carlos F. Barbas III、D. B. Ramachary、Naidu S. Chowdari

  DOI：10.1055/s-2003-41486

  日期：——

  component hetero-domino Knoevenagel-Diels-Alder-Epimerization reactions of readily available precursors enones la-i, arylaldehydes 2a-i and 1,3-indandione 3 to furnish highly substituted prochiral spiro[cyclo-hexane-1,2'-indan]-1',3',4-triones 5a-i in a highly diastereoselective fashion with excellent yields. We demonstrate the first L-proline and pyrrolidine catalyzed epimerization reactions of transspiranes

  L-脯氨酸和吡咯烷催化易于获得的前体烯酮 la-i、芳醛 2a-i 和 1,3-茚满二酮 3 的三组分杂多米诺 Knoevenagel-Diels-Alder-差向异构化反应，以提供高度取代的前手性螺[环己烷-1,2'-indan]-1',3',4-triones 5a-i 以高度非对映选择性的方式具有优异的产率。我们展示了第一个 L-脯氨酸和吡咯烷催化的反式螺环 6a-i 到顺式螺环 5a-i 的差向异构化反应。前手性螺环 5a-i 是合成苯甲酰化的中心聚喹烷的优良原料。
• Kuck, Dietmar, Chemische Berichte, 1994, vol. 127, # 2, p. 409 - 426
  作者：Kuck, Dietmar

  DOI：——

  日期：——
• Benzoannelated centropolyquinanes. 2. (all-cis)-Tetrabenzotetracyclo[5.5.1.04,13.010,13]tridecane, "fenestrindan"
  作者：Dietmar. Kuck、Hartmut. Boegge

  DOI：10.1021/ja00285a048

  日期：1986.12
• KUCK D.; BOGGE H., J. AMER. CHEM. SOC., 108,(1986) N 25, 8107-8109
  作者：KUCK D.、 BOGGE H.

  DOI：——

  日期：——
• Benzoannelatedcis,cis,cis,trans-[5.5.5.6]Fenestranes: Syntheses, Base Lability, and Flattened Molecular Structure of Strained Epimers of the all-cis Series
  作者：Björn Bredenkötter、Ulrich Flörke、Dietmar Kuck

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

  日期：2001.8.3

  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.