3,4-diacetyl-14,19-dioxatetracyclo[20.4.0.0(2,7).0(6,11)]hexacosa-2,4,6,8,10,22,24,26-octaene-13,20-dione | 1269806-42-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: 3,4-diacetyl-14,19-dioxatetracyclo[20.4.0.0(2,7).0(6,11)]hexacosa-2,4,6,8,10,22,24,26-octaene-13,20-dione
• 英文别名: 3,4-Diacetyl-14,19-dioxatetracyclo[20.4.0.02,7.06,11]hexacosa-1(26),2,4,6(11),7,9,22,24-octaene-13,20-dione
• CAS: 1269806-42-9
• 化学式: C₂₈H₂₆O₆
• 分子量: 458.511
• InChiKey: XXMFQUFACWMGIG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2-碘苯乙酸 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 硫酸 、 戴斯-马丁氧化剂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 丙酮 、 叔丁醇 为溶剂， 反应 5.0h， 生成 3,4-diacetyl-14,19-dioxatetracyclo[20.4.0.0(2,7).0(6,11)]hexacosa-2,4,6,8,10,22,24,26-octaene-13,20-dione
  参考文献：
  名称：

  Preparation of Strained Axially Chiral (1,5)Naphthalenophanes by Photo-dehydro-Diels−Alder Reaction

  摘要：

  The preparation of 10 (1,5)naphthalenophanes (10a-j) by photo-dehydro-Diels-Alder (PDDA) reaction is described. Owing to hindered rotation around the biaryl axis, compounds 10 are axially chiral and the separation of enantiomers by chiral HPLC was demonstrated in three cases (10a,b,e). The absolute configuration of the isolated enantiomers could be unambiguously determined by comparison of calculated and measured circular dichroism (CD) spectra. Furthermore, we analyzed ring strain phenomena of (1,5)naphthalenophanes 10. Depending on the length of the linker units, one can distinguish three classes of naphthalenophanes. Compounds 10a-c are highly strained (E-STR = 7-31 kcal/mol), and the strain is caused by small bond angles in the linker unit and deformation of the naphthalene moiety. Another type of strain is observed if the linker unit becomes relatively long (10g,h) originating from transannular interactions and is comparable with the well-known strain of medium sized rings. The naphthalenophanes 10d-f with a linker length of 10-14 atoms are only marginally strained. To clearly discriminate the different sources of strain, we defined two geometrical parameters (average central dihedral angle delta(C) and naphthalene thickness D-N) and demonstrated that they are well-suited to indicate naphthalene deformation of our naphthalenophanes 10 as well as of ten model naphthalenophanes (I-X) with different linker lengths and linking positions.

  DOI：

  10.1021/ja109118m

文献信息

• Preparation of Strained Axially Chiral (1,5)Naphthalenophanes by Photo-dehydro-Diels−Alder Reaction
  作者：Pablo Wessig、Annika Matthes

  DOI：10.1021/ja109118m

  日期：2011.3.2

  The preparation of 10 (1,5)naphthalenophanes (10a-j) by photo-dehydro-Diels-Alder (PDDA) reaction is described. Owing to hindered rotation around the biaryl axis, compounds 10 are axially chiral and the separation of enantiomers by chiral HPLC was demonstrated in three cases (10a,b,e). The absolute configuration of the isolated enantiomers could be unambiguously determined by comparison of calculated and measured circular dichroism (CD) spectra. Furthermore, we analyzed ring strain phenomena of (1,5)naphthalenophanes 10. Depending on the length of the linker units, one can distinguish three classes of naphthalenophanes. Compounds 10a-c are highly strained (E-STR = 7-31 kcal/mol), and the strain is caused by small bond angles in the linker unit and deformation of the naphthalene moiety. Another type of strain is observed if the linker unit becomes relatively long (10g,h) originating from transannular interactions and is comparable with the well-known strain of medium sized rings. The naphthalenophanes 10d-f with a linker length of 10-14 atoms are only marginally strained. To clearly discriminate the different sources of strain, we defined two geometrical parameters (average central dihedral angle delta(C) and naphthalene thickness D-N) and demonstrated that they are well-suited to indicate naphthalene deformation of our naphthalenophanes 10 as well as of ten model naphthalenophanes (I-X) with different linker lengths and linking positions.