(2R,6S)-2,6-diphenylspiro[cyclohexane-1,2′-indene]-1′,3′,4-trione | 19294-95-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (2R,6S)-2,6-diphenylspiro[cyclohexane-1,2′-indene]-1′,3′,4-trione
• 英文别名: (2β,6β)-2,6-diphenylspiro[cyclohexane-1,2'-indene]-1',3',4-trione；(2β,6β)-2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione；2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione；trans-1.3-Diphenyl-2.2-spiro-phthaloyl-cyclohexanon-(5)；(3S,5R)-3,5-diphenylspiro[cyclohexane-4,2'-indene]-1,1',3'-trione
• CAS: 19294-95-2
• 化学式: C₂₆H₂₀O₃
• 分子量: 380.443
• InChiKey: JCRKSTFTQQLWFT-ZRZAMGCNSA-N

物化性质

• 熔点：
  225 °C
• 沸点：
  608.0±55.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

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：

  (2R,6S)-2,6-diphenylspiro[cyclohexane-1,2′-indene]-1′,3′,4-trione 在 亚硝基苯 、 L-脯氨酸 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以63%的产率得到(2S,3R,6R)-3-hydroxy-2,6-diphenylspiro[cyclohexane-1,2'-indan]-1',3',4-trione
  参考文献：
  名称：

  Direct Amino Acid-Catalyzed Asymmetric Desymmetrization of meso-Compounds:  Tandem Aminoxylation/O−N Bond Heterolysis Reactions

  摘要：

  A practical organocatalytic process for the synthesis of optically active, highly substituted (x-hydroxy-ketones was achieved through asymmetric desymmetrization (ADS) of prochiral ketones. The ADS and O-N bond reduction reaction of prochiral ketone with nitrosobenzene in the presence of a catalytic amount of chiral amine or amino acid produced the tandem ADS/O-N bond reduced products as single diastereomers with good yields and excellent enantiomeric excesses.

  DOI：

  10.1021/ol050246e
• 作为产物：
  描述：

  苄叉丙酮 、 2-(苯基亚甲基)茚-1,3-二酮 在 L-脯氨酸 作用下， 以 甲醇 为溶剂， 反应 96.0h， 生成 (2R,6S)-2,6-diphenylspiro[cyclohexane-1,2′-indene]-1′,3′,4-trione
  参考文献：
  名称：

  第一次有机催化杂-多米诺-多米诺-狄尔斯-阿尔德-差向异构化反应：高度取代的螺[环己烷-1,2'-茚满]-1',3',4-三酮的非对映选择性合成

  摘要：

  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。

  DOI：

  10.1055/s-2003-41486

文献信息

• Direct Organocatalytic Asymmetric Heterodomino Reactions:  The Knoevenagel/Diels−Alder/Epimerization Sequence for the Highly Diastereoselective Synthesis of Symmetrical and Nonsymmetrical Synthons of Benzoannelated Centropolyquinanes
  作者：D. B. Ramachary、K. Anebouselvy、Naidu S. Chowdari、Carlos F. Barbas

  DOI：10.1021/jo049581r

  日期：2004.9.1

  Amino acids and amines have been used to catalyze three component hetero-domino Knoevenagel/Diels−Alder/epimerization reactions of readily available various precursor enones (1a−l), aldehydes (2a−p), and 1,3-indandione (3). The reaction provided excellent yields of highly substituted, symmetrical and nonsymmetrical spiro[cyclohexane-1,2‘-indan]-1‘,3‘,4-triones (5) in a highly diastereoselective fashion

  氨基酸和胺已用于催化易得的各种前体烯酮（1a - l），醛（2a - p）和1,3-茚满二酮（3）的三组分异多米诺Knoevenagel / Diels-Alder /异构化反应。该反应以对映体选择性低至中等的高度非对映选择性提供了极高产率的高度取代的，对称和非对称的螺环己烷-1，2 -'-茚满-1'，3'，4-三酮（5）。芳基醛（2a - p）和1,3-茚满二酮（3）的Knoevenagel缩合反应在有机催化下提供了亚芳基1,3-茚满二酮（17），收益率很高。我们首次证明了反式-螺烷（6）对顺式螺烷（5）的氨基酸和胺催化的差向异构反应。反式-螺环烷（6）转化为顺式螺环烷5的机理显示为通过逆迈克尔/迈克尔反应进行，而不是通过分离顺式螺环烷的吗啉烯胺中间体（22）进行去质子化/再质子化。前手性顺式螺环烷（5ab）和反式螺环烷（6ab）是合成苯甲酰化的中心聚奎宁烷的极好原料。在氨基酸和胺的催化
• Expanding the Scope of Primary Amine Catalysis: Stereoselective Synthesis of Indanedione-Fused 2,6-Disubstituted <i>trans-</i>Spirocyclohexanones
  作者：G. Madhusudhan Reddy、Chi-Ting Ko、Kai-Hong Hsieh、Chia-Jui Lee、Utpal Das、Wenwei Lin

  DOI：10.1021/acs.joc.5b02921

  日期：2016.3.18

  A cinchona-alkaloid-derived chiral primary-amine-catalyzed enantioselective method for the synthesis of the thermodynamically less stable indanedione-fused 2,6-trans-disubstituted spirocyclohexanones is demonstrated. Both the enantiomeric forms of the trans isomer are obtained in excellent yields and enantioselectivities. Furthermore, one of the enantiopure trans-spiranes bearing an additional α-substitution

  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。
• 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.
• Identification of Biphenyl-Based Hybrid Molecules Able To Decrease the Intracellular Level of Bcl-2 Protein in Bcl-2 Overexpressing Leukemia Cells
  作者：Daniela Pizzirani、Marinella Roberti、Stefania Grimaudo、Antonietta Di Cristina、Rosaria Maria Pipitone、Manlio Tolomeo、Maurizio Recanatini

  DOI：10.1021/jm900907s

  日期：2009.11.12

  With the aim of enhancing the structural complexity and diversity of an existing collection of bi- and terphenyl compounds, we synthesized hybrid molecules comprising of spirocyclic ketones (a complexity-bearing core) and bi/terphenyls (privileged fragments). Compounds 1, 3, 4, and 6 showed well-defined activity on apoptosis and differentiation, making them potential leads for development as new anticancer agents and chemical probes to study signaling networks in neoplastic cells.
• 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。