Copper Causes Regiospecific Formation of C4F8-Containing Six-Membered Rings and their Defluorination/Aromatization to C4F4-Containing Rings in Triphenylene/1,4-C4F8I2 Reactions

被引：13
|
作者：
Rippy, Kerry C. [1 ]
Bukovsky, Eric V. [1 ]
Clikeman, Tyler T. [1 ]
Chen, Yu-Sheng [2 ]
Hou, Gao-Lei [3 ]
Wang, Xue-Bin [3 ]
Popov, Alexey A. [4 ]
Boltalina, Olga V. [1 ]
Strauss, Steven H. [1 ]
机构：
[1] Colorado State Univ, Dept Chem, Ft Collins, CO 80523 USA
[2] Univ Chicago Adv Proton Source, ChemMatCARS, Argonne, IL 60439 USA
[3] Pacific NW Natl Lab, Div Phys Sci, Richland, WA 99352 USA
[4] Leibniz Inst Solid State & Mat Res, D-01069 Dresden, Germany
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 03期
基金：
美国国家科学基金会;
关键词：
aromatization; copper; perfluoroalkylation; triphenylene; X-ray structure; F BOND ACTIVATION; ARENE-PERFLUOROARENE INTERACTIONS; ORGANIC SEMICONDUCTORS; RADICAL PERFLUOROALKYLATION; RATE CONSTANTS; FLUOROALKYLATION; CORANNULENE; CYCLIZATION; AROMATICS; REAGENTS;
D O I：
10.1002/chem.201504291
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4F8I2 at 360 degrees C led to regiospecific substitution of TRPH ortho C(beta) atoms to form C4F8-containing rings, completely suppressing substitution on C(alpha) atoms. In addition, Cu caused selective reductive-defluorination/aromatization (RD/A) to form C4F4-containing aromatic rings. Without Cu, the reactions of TRPH and 1,4-C4F8I2 were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cu-promoted 1) regiospecific perfluoroannulation, 2) preparative C-F activation, and 3) RD/A. HPLC-purified products were characterized by X-ray diffraction, low-temperature PES, and H-1/F-19 NMR.
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页码：874 / 877
页数：4
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