2-trimethylsilylcorannulenyl triflate | 1050685-38-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 2-trimethylsilylcorannulenyl triflate
• 英文别名: 2-trimethylsilylcorannulenyl trifluoromethanesulfonate；corannulyne；(3-Trimethylsilyl-2-hexacyclo[11.5.2.04,17.07,16.010,15.014,18]icosa-1(18),2,4(17),5,7(16),8,10(15),11,13,19-decaenyl) trifluoromethanesulfonate；(3-trimethylsilyl-2-hexacyclo[11.5.2.04,17.07,16.010,15.014,18]icosa-1(18),2,4(17),5,7(16),8,10(15),11,13,19-decaenyl) trifluoromethanesulfonate
• CAS: 1050685-38-5
• 化学式: C₂₄H₁₇F₃O₃SSi
• 分子量: 470.544
• InChiKey: XAJUGRHATWSHOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.54
• 重原子数：
  32
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-trimethylsilylcorannulenyl triflate 在 tris-(dibenzylideneacetone)dipalladium(0) 、 cesium fluoride 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 12.0h， 以40%的产率得到Nonadecacyclo[47.5.2.27,13.225,31.04,53.05,42.06,23.08,12.09,22.010,19.011,16.024,41.026,30.027,40.028,37.029,34.043,52.046,51.050,54]hexaconta-1(54),2,4(53),5,7,9(22),10(19),11(16),12,14,17,20,23,25,27(40),28(37),29(34),30,32,35,38,41,43(52),44,46(51),47,49,55,57,59-triacontaene
  参考文献：
  名称：

  Corannulyne 的 Cyclotrimerization：空间位阻调节 Corannulene 碗的反转障碍

  摘要：

  X 射线晶体结构测定和 HDFT 计算表明，钯催化的由 2-三甲基甲硅烷基三氟甲磺酸基三氟甲磺酸酯生成的二甲萘醌环三聚反应产生了一种 C60H24 烃，它更喜欢 C1 对称的高度非平面“扭曲”构象。它的三个冠烯亚基在理想化的 D3h 对称性中相同，表现出截然不同的反转势垒（从 8.4 到 17.3 kcal mol-1），由高度不对称结构内的空间拥挤调节。具有最低活化势垒的蒌烯单元的碗对碗反转导致分子的假旋转并产生仅显示 12 个不同质子信号的 1H NMR 光谱。选定的 NMR 信号的线形分析给出了 8.5-8.6 kcal mol-1 的势垒估计。

  DOI：

  10.1002/ejoc.201101374
• 作为产物：
  描述：

  三氟甲磺酸酐 、 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.33h， 以710 mg的产率得到2-trimethylsilylcorannulenyl triflate
  参考文献：
  名称：

  2-Trimethylsilylcorannulenyl Trifluoromethanesulfonate: An Efficient Precursor for 1,2-Didehydrocorannulene

  摘要：

  2-Trimethylsilylcorannulenyl trifluoromethanesulfonate, prepared from bromocorannulene, provides a means for generating of 1,2-didehydrocorannulene (corannulyne) under very mild conditions as demonstrated by the high-yield formation of its adducts with dienes.

  DOI：

  10.1021/ol801581z

文献信息

• Tuning the Properties of Corannulene-Based Polycyclic Aromatic Hydrocarbons by Varying the Fusing Positions of Corannulene
  作者：Qi Xu、Chu Wang、Yu Zhao、Dan Zheng、Chengyuan Shao、Weijie Guo、Xuebin Deng、Ying Wang、Xuebo Chen、Jun Zhu、Hua Jiang

  DOI：10.1021/acs.orglett.0c02754

  日期：2020.9.18

  derivative to the rim and flank bonds of corannulene generated 4 and 7, respectively, which underwent a Scholl reaction to provide novel distorted PAHs CORA-1 and CORA-2, consisting of corannulene and dibenzocoronene units with different connections between them. The studies revealed that the properties of these PAHs are highly dependent on the fusing positions of corannulene.

  pyr衍生物与cor喃环的边缘和侧面键的选择性融合分别产生了4和7，它们进行了Scholl反应，以提供新的扭曲的PAHs CORA-1和CORA-2，其由cor环烯和二苯并co烯单元组成，它们之间具有不同的连接。研究表明，这些多环芳烃的性质高度依赖于香兰素的融合位置。
• A Distorted Hybrid Corannulene–Dibenzobistetracene
  作者：Qi Xu、Chu Wang、Dan Zheng、Jing He、Ying Wang、Xuebo Chen、Hua Jiang

  DOI：10.1021/acs.joc.0c03065

  日期：2021.10.15

  We have designed and synthesized a new type of distorted nanographene by Diels–Alder and Scholl reactions that contains one dibenzobistetracene (DBT, 1) core and two end-capping corannulene units. Single-crystal X-ray diffraction analyses demonstrate that nanographene 1 contains two [5] helicene subunits with a dihedral angle of 62°, consequently leading to the distorted DBT core. In addition, the

  我们通过 Diels-Alder 和 Scholl 反应设计并合成了一种新型扭曲纳米石墨烯，它包含一个二苯并双并四苯(DBT, 1 ) 核和两个封端的芴烯单元。单晶 X 射线衍射分析表明，纳米石墨烯1包含两个 [5] 螺旋烯亚基，二面角为 62°，因此导致 DBT 核变形。此外，通过吸收和发射光谱结合理论计算研究了1的光物理性质和（非）芳香性。
• Molecular clips and tweezers with corannulene pincers
  作者：Lesya Kobryn、William P. Henry、Frank R. Fronczek、Renata Sygula、Andrzej Sygula

  DOI：10.1016/j.tetlet.2009.09.177

  日期：2009.12

  Application of the synthetic methodology developed in our laboratory yields molecular clips and tweezers with corannulene pincers and cyclooctadiene or cyclooctatetraene tethers. These highly nonplanar systems possess a potential for binding guest molecules of various sizes. One of the clips, bis(benzocorannulene)[a,e]cyclooctadiene, exists in a 'open' chair conformation encapsulating solvating nitrobenzene in the solid state, while it is expected to prefer an internally pi-pi stacked twist-boat conformation in the gas phase. (c) 2009 Elsevier Ltd. All rights reserved.
• Corannulene Subunit Acts as a Diene in a Cycloaddition Reaction: Synthesis of C₈₀H₃₂ Corannulyne Tetramer
  作者：Michael Yanney、Frank R. Fronczek、Andrzej Sygula

  DOI：10.1021/ol302274j

  日期：2012.9.21

  Distortion of six-membered rings in corannulene subunits of corannulyne (1,2-didehydrocorannulene) cyclotrimer activates the system for a cycloaddition reaction with another corannulyne unit. This unprecedented cycloaddition in which a corannulene fragment acts as a diene produces the largest oligomer of corannulyne reported to date. X-ray crystallography reveals the highly nonplanar structure of the tetramer which exhibits conformational and optical absorption properties very different from those of the cyclotrimer.
• 2-Trimethylsilylcorannulenyl Trifluoromethanesulfonate: An Efficient Precursor for 1,2-Didehydrocorannulene
  作者：Andrzej Sygula、Renata Sygula、Lesya Kobryn

  DOI：10.1021/ol801581z

  日期：2008.9.1

  2-Trimethylsilylcorannulenyl trifluoromethanesulfonate, prepared from bromocorannulene, provides a means for generating of 1,2-didehydrocorannulene (corannulyne) under very mild conditions as demonstrated by the high-yield formation of its adducts with dienes.