(1RS,2SR,3SR,3aRS,8aRS)-1,3-diphenyl-3a,8a-dihydrospiro{cyclopenta[a]indene-2,2'(1H,3'H)-indene}-1',8(3H)-dione

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (1RS,2SR,3SR,3aRS,8aRS)-1,3-diphenyl-3a,8a-dihydrospiro{cyclopenta[a]indene-2,2'(1H,3'H)-indene}-1',8(3H)-dione
• 英文别名: (1RS,2SR,3SR,3aRS,8aRS)-1,3-diphenyl-3a,8a-dihydrospiro{cyclopenta[a]indene-2,2'-(1H,3'H)indene}-1',8(3H)-dione；(1S,2S,3R,3aR,8bR)-1,3-diphenylspiro[1,3,3a,8b-tetrahydrocyclopenta[a]indene-2,2'-3H-indene]-1',4-dione
• 化学式: C₃₂H₂₄O₂
• 分子量: 440.541
• InChiKey: DERYTOHQOBYDNH-IROWRPIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (E)-2-benzylidene-2,3-dihydro-1H-inden-1-one 在 碳酸胍 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 5.5h， 生成 (1RS,2SR,3SR,3aRS,8aRS)-1,3-diphenyl-3a,8a-dihydrospiro{cyclopenta[a]indene-2,2'(1H,3'H)-indene}-1',8(3H)-dione
  参考文献：
  名称：

  Studies on the Dimerization of 2-Benzylidene-1-indanone

  摘要：

  It has been observed that 2-(E)-benzylidene-1-indanone (1) undergoes dimerization under basic conditions. The reaction is highly stereoselective and provides almost exclusively dimer 2b using NaHCO3/DMF, guanidine carbonate/DMF, or Cs2CO3/CH3CN. The structure and the relative stereochemistry of compound 2b were initially established on the basis of COSY, HMQC, HMBC, and NOESY NMR correlation techniques. The structure and the stereochemistry were then confirmed by X-ray crystallographic analysis. Two other stereoisomers were obtained, in minor proportions, by varying the experimental conditions. A fourth isomer was also produced using 2-(Z)-benzylidene-1-indanone as the starting material.

  DOI：

  10.1021/jo970402y

文献信息

• Highly Diastereoselective One-Pot Synthesis of Spiro{cyclopenta[<i>a</i>]indene-2,2‘-indene}diones from 1-Indanones and Aromatic Aldehydes
  作者：Pelayo Camps、Luis R. Domingo、Xavier Formosa、Carles Galdeano、Diana González、Diego Muñoz-Torrero、Sílvia Segalés、Mercè Font-Bardia、Xavier Solans

  DOI：10.1021/jo0600095

  日期：2006.4.1

  has been studied using DFT methods at the B3LYP/6-31G* level. The dimerization takes place through a process involving a Michael addition of a carbanion, obtained by deprotonation of 5g at the 3-position, to a second molecule of 5g, followed by an intramolecular Michael addition in the corresponding intermediate. The final protonation of the resulting anion accounts for the formation of the cis-fused

  在THF中用芳族醛和NaOEt处理1-茚满酮可通过四组分反应提供复杂的螺多环化合物，其中每种起始化合物的两个分子结合形成四个新的碳-碳键，从而形成了一个新的五个-元环，带有五个连续的立体定位中心，具有明确定义的相对构型。还形成了不同量的主要产物的次要差向异构体。茚满酮组分中甲氧基取代基的存在以及衍生自π-过量杂环的醛的使用使二聚步骤变慢了。在这些情况下，从预制的烯酮开始可获得更好的螺二聚体收率。该反应似乎是通过这样形成的烯酮的交叉羟醛缩合，脱水和二聚而发生的。已经使用DFT方法在B3LYP / 6-31G *水平上研究了5g。二聚化是通过以下过程进行的：将在3位的5g去质子化的碳负离子迈克尔加成至5g的第二个分子，然后在相应的中间体中进行分子内迈克尔加成。最终阴离子的最终质子化解释了顺式融合的五环系统的形成。
• Dimerization of conjugated 1-indanones
  作者：Yves Leblanc、Claude Dufresne、Rajiv Dhawan、Jason Ollerenshaw、Adam Littke、Laird A Trimble、Nancy N Tsou

  DOI：10.1139/v99-236

  日期：2000.6.1

  Conjugated 1-indanones dimerize under basic conditions to provide spirodimers. For example when 2-(E)-carbomethoxymethylene-1-indanone (5) was treated with Cs₂CO₃ in CH₃CN, two spirodimers, 6 and 7, were produced via two modes of reaction (mode A and mode B). With 2-(E)-cyanomethylene-1-indanone (9) only mode A dimerized spiro products (10 and 11) were observed whereas with 2-chloromethylidene-1-indanone (12) a 1,2-dimer (13) was obtained instead of the expected spirodimer.Key words: dimerization, conjugated 1-indanones, spirodimers.

  共轭的1-吲哚酮在碱性条件下发生二聚反应，形成螺环二聚体。例如，当2-(E)-羰甲氧基亚甲基-1-吲哚酮（5）在CH3CN中与Cs2CO3反应时，通过两种反应方式（方式A和方式B）产生了两种螺环二聚体，6和7。使用2-(E)-氰甲亚甲基-1-吲哚酮（9）时，只观察到方式A发生二聚反应形成的螺环产物（10和11），而使用2-氯甲基亚甲基-1-吲哚酮（12）时，得到了1,2-二聚体（13），而不是预期的螺环二聚体。关键词：二聚化，共轭的1-吲哚酮，螺环二聚体。
• Synthesis of benzylidenecycloalkan-1-ones and 1,5-diketones under Claisen–Schmidt reaction: Influence of the temperature and electronic nature of arylaldehydes
  作者：Beatriz Lantaño、José M. Aguirre、Eleonora V. Drago、Mariela Bollini、Diego J. de la Faba、Jorge D. Mufato

  DOI：10.1080/00397911.2017.1367819

  日期：2017.12.2

  involves Michael addition reaction, which is also dependent on the temperature. Theoretical studies using density-functional theory allowed understanding the chemical reactivity and the site selectivity of α,β-enones used in this work through the calculation of global and local electrophilicity on C–β. Both the electrophilicity of C-β and the temperature led the course of reaction toward the formation of

  摘要 在此，我们展示了在经典 Claisen-Schmidt 缩合条件下苯并环烷-1-酮和芳醛反应中反应温度和芳醛电子性质的影响结果。通过多组分反应获得的苯并环烷烃-1-酮和/或螺多环-1,5-二酮的2-亚芳基衍生物取决于芳醛的电子性质和反应温度。此外，在相同条件下，2-亚芳基茚满-1-酮通过涉及迈克尔加成反应的过程提供双-茚满-1,5-二酮，该过程也取决于温度。使用密度泛函理论的理论研究可以理解 α 的化学反应性和位点选择性，通过计算 C-β 上的全局和局部亲电性，本工作中使用的 β-烯酮。C-β 的亲电性和温度导致反应过程朝着形成羟醛缩合、羟醛缩合/迈克尔加成和羟醛缩合/二聚产物的方向发展。这项工作是第一个对双茚满 1,5-二酮进行结构和构型分配的工作。图形概要
• Studies on the Dimerization of 2-Benzylidene-1-indanone
  作者：Carl Berthelette、Chris McCooye、Yves Leblanc、Laird A. Trimble、Nancy N. Tsou

  DOI：10.1021/jo970402y

  日期：1997.6.1

  It has been observed that 2-(E)-benzylidene-1-indanone (1) undergoes dimerization under basic conditions. The reaction is highly stereoselective and provides almost exclusively dimer 2b using NaHCO3/DMF, guanidine carbonate/DMF, or Cs2CO3/CH3CN. The structure and the relative stereochemistry of compound 2b were initially established on the basis of COSY, HMQC, HMBC, and NOESY NMR correlation techniques. The structure and the stereochemistry were then confirmed by X-ray crystallographic analysis. Two other stereoisomers were obtained, in minor proportions, by varying the experimental conditions. A fourth isomer was also produced using 2-(Z)-benzylidene-1-indanone as the starting material.