3,8-Di-tert-butyl-1,10-diiodo-11,12-dihydro-11,12-diaza-indeno[2,1-a]fluorene | 876124-86-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 3,8-Di-tert-butyl-1,10-diiodo-11,12-dihydro-11,12-diaza-indeno[2,1-a]fluorene
• 英文别名: 3,8-Ditert-butyl-1,10-diiodo-11,12-dihydroindolo[2,3-a]carbazole
• CAS: 876124-86-6
• 化学式: C₂₆H₂₆I₂N₂
• 分子量: 620.315
• InChiKey: FLRODJQHRIKZJB-UHFFFAOYSA-N

物化性质

• 沸点：
  680.7±50.0 °C(Predicted)
• 密度：
  1.722±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  31.6
• 氢给体数：
  2
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3,8-Di-tert-butyl-1,10-diiodo-11,12-dihydro-11,12-diaza-indeno[2,1-a]fluorene 在 copper(l) iodide 、 potassium carbonate 、 三乙胺 、 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 34.0h， 生成 3-[2-(3,8-ditert-butyl-10-ethynyl-11,12-dihydroindolo[2,3-a]carbazol-1-yl)ethynyl]-N-[(1S)-1-phenylethyl]benzamide
  参考文献：
  名称：

  一种基于折叠体的手性分子开关，在阴离子结合时显示螺旋感的完全反转

  摘要：

  手性吲哚并咔唑二聚体通过分子内氢键折叠成螺旋构象，如 (1) H NMR 和 CD 光谱以及旋光所示。特别是，发现二聚体的光学性质对溶剂的性质极其敏感，这取决于它们是否折叠。二聚体的螺旋方向可以通过结合硫酸根离子可逆地转换，这会导致 CD 光谱的完全反转。硫酸盐配合物的结合模式和绝对立体化学由单晶 X 射线结构明确确定，这与溶液中的 CD 和 (1) H NMR 光谱一致。

  DOI：

  10.1021/ja206546b
• 作为产物：
  描述：

  5,5'-di(tert-butyl)-7,7'-diiodo-2,2'-biindolyl 、 二甲氨基乙醛缩二乙醇 以 溶剂黄146 为溶剂， 反应 2.0h， 以68%的产率得到3,8-Di-tert-butyl-1,10-diiodo-11,12-dihydro-11,12-diaza-indeno[2,1-a]fluorene
  参考文献：
  名称：

  Biindolyl-based molecular clefts that bind anions by hydrogen-bonding interactions

  摘要：

  Molecular clefts were synthesized from 2,2'-biindolyl scaffold that contains good hydrogen bond donors of two indole NHs. The molecular clefts were systematically modified in two different manners to increase binding affinities toward chloride. The association constant dramatically increased when additional hydrogen-bonding sites of two benzamide units were incorporated to the biindolyl scaffold. For example, the association constants of 1a and 1b are 5.1 x 10(3) and 1.4 x 10(4) M-1 in CH3CN at 22 +/- 1 degrees C, while reference molecule 10 having only two indole NHs showed the association constant of 340 M-1 under the same conditions. When the biindolyl backbone was structurally preorganized, the binding affinities toward anions were further increased with additional stabilization energy (-Delta Delta G) of 2.0 +/- 0.2 kcal/mol). (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.06.157

文献信息

• Selective sulfate binding induces helical folding of an indolocarbazole oligomer in solution and solid state
  作者：Jun-il Kim、Hemraj Juwarker、Xinfang Liu、Myoung Soo Lah、Kyu-Sung Jeong

  DOI：10.1039/b919519j

  日期：——

  Hydrogen bonding to anions drives the helical folding of an indolocarbazole oligomer, thus resulting in an internal cavity with six NHs and two OHs for binding sulfate with high selectivity.

  氢与阴离子的键合驱动吲哚并咔唑低聚物的螺旋折叠，从而形成一个内腔，其中有六个NH和两个OH以高选择性结合硫酸盐。
• An Indolocarbazole Trimer with an Expanded Cavity for Anion Binding
  作者：Jae-min Suk、Jun-il Kim、Kyu-Sung Jeong

  DOI：10.1002/asia.201100087

  日期：2011.8.1

  An indolocarbazole trimer that consists of three indolocarbazoles linked by butadiynyl units has been prepared as an anion receptor (see picture). This trimer folds into a helical conformation upon anion binding by multiple hydrogen bonds. Compared with its analog that has shorter ethynyl linkers, the receptor shows much increased affinities to large anions such as dihydrogen phosphate and acetate

  由阴离子丁二酰基单元连接的三个吲哚并咔唑组成的吲哚并咔唑三聚体已被制备为阴离子受体（见图）。该三聚体在通过多个氢键与阴离子结合后折叠成螺旋构象。与具有较短乙炔基接头的类似物相比，该受体与大阴离子（如磷酸二氢盐和乙酸盐）的亲和力大大提高。
• A helically twisted imine macrocycle that allows for determining the absolute configuration of α-amino carboxylates
  作者：Min Jun Kim、Ye Rin Choi、Hae-Geun Jeon、Philjae Kang、Moon-Gun Choi、Kyu-Sung Jeong

  DOI：10.1039/c3cc46754f

  日期：——

  Binding of α-amino carboxylates to a helically twisted imine macrocycle based on the indolocarbazole scaffold gives rise to characteristic circular dichroism spectra, and the patterns of the Cotton effects are consistent with the absolute configuration of α-amino carboxylates.

  α-氨基羧酸盐与基于吲哚并咔唑支架的螺旋扭曲亚胺大环的结合产生特征圆二色性光谱，并且Cotton效应的模式与α-氨基羧酸盐的绝对构型一致。
• Stereospecific control of the helical orientation of indolocarbazole–pyridine hybrid foldamers by rational modification of terminal chiral appendages
  作者：Junyoung Kim、Hae-Geun Jeon、Philjae Kang、Kyu-Sung Jeong

  DOI：10.1039/c7cc03552g

  日期：——

  The helical handedness excess of an indolocarbazole–pyridine hybrid oligomer capable of folding into a stable helical structure was achieved up to 96% by rational modification of terminal chiral residues.

  通过合理修饰末端手性残基，可以折叠成稳定螺旋结构的吲哚并咔唑-吡啶杂化低聚物的螺旋惯性达到了96％以上。
• Template‐Directed Quantitative One‐Pot Synthesis of Homochiral Helical Receptors Enabling Enantioselective Binding
  作者：Kyung Mog Kim、Geunmoo Song、Seungwon Lee、Hae‐Geun Jeon、Woojeong Chae、Kyu‐Sung Jeong

  DOI：10.1002/anie.202011230

  日期：2020.12.7

  homochiral helical cavities inside aromatic foldamers. One‐handed helical receptors P‐1, M‐1, P‐2 and M‐2 were assembled from their precursors in the presence of appropriate templates (d‐ and l‐tartaric acid, and d‐ and l‐sorbitol, respectively) via three sequential steps in one pot: imine‐linked chain elongation, template‐induced folding and [4+2] cycloaddition between helical turns. These helical receptors

  实施了模板指导的合成和动态共价化学，以实现芳香族折叠子内部同手性螺旋腔的定量一锅合成。单向螺旋受体P- 1，M- 1，P- 2和M- 2在合适的模板（d-和l-酒石酸以及d-和l-山梨糖醇）通过一个锅中的三个连续步骤进行操作：亚胺连接的链伸长，模板诱导的折叠和螺旋匝之间的[4 + 2]环加成。这些螺旋受体被证明能对映选择性地结合用作模板的手性客体，并且对映体客体的缔合常数之间的差异高达两个数量级以上。受体的结构和结合模式已通过单晶X射线晶体学和1 H NMR光谱进行了全面表征。