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

Abstract

The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4F8I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4F8-containing rings, completely suppressing substitution on C(α) 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 Cupromoted (i) regiospecific perfluoroannulation, (ii) preparative C–F activation, and (iii) RD/A. HPLC-purified products were characterized by X-ray diffraction, low-temperature PES, and 1H/19F NMR.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1243208
Report Number(s):
PNNL-SA-111662
Journal ID: ISSN 1521-3765; 48349; KC0301050
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry - A European Journal (Online); Journal Volume: 22; Journal Issue: 3
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Rippy, Kerry C., Bukovsky, Eric V., Clikeman, Tyler T., Chen, Yu-Sheng, Hou, Gao-Lei, Wang, Xue B., Popov, Alexey, Boltalina, Olga V., and Strauss, Steven H. Copper Causes Regiospecific Formation of C4F8-Containing Six-Membered Rings and their Defluorination/Aromatization to C4F4-Containing Rings in Triphenylene/1,4-C4F8I2 Reactions. United States: N. p., 2016. Web. doi:10.1002/chem.201504291.
Rippy, Kerry C., Bukovsky, Eric V., Clikeman, Tyler T., Chen, Yu-Sheng, Hou, Gao-Lei, Wang, Xue B., Popov, Alexey, Boltalina, Olga V., & Strauss, Steven H. Copper Causes Regiospecific Formation of C4F8-Containing Six-Membered Rings and their Defluorination/Aromatization to C4F4-Containing Rings in Triphenylene/1,4-C4F8I2 Reactions. United States. doi:10.1002/chem.201504291.
Rippy, Kerry C., Bukovsky, Eric V., Clikeman, Tyler T., Chen, Yu-Sheng, Hou, Gao-Lei, Wang, Xue B., Popov, Alexey, Boltalina, Olga V., and Strauss, Steven H. 2016. "Copper Causes Regiospecific Formation of C4F8-Containing Six-Membered Rings and their Defluorination/Aromatization to C4F4-Containing Rings in Triphenylene/1,4-C4F8I2 Reactions". United States. doi:10.1002/chem.201504291.
@article{osti_1243208,
title = {Copper Causes Regiospecific Formation of C4F8-Containing Six-Membered Rings and their Defluorination/Aromatization to C4F4-Containing Rings in Triphenylene/1,4-C4F8I2 Reactions},
author = {Rippy, Kerry C. and Bukovsky, Eric V. and Clikeman, Tyler T. and Chen, Yu-Sheng and Hou, Gao-Lei and Wang, Xue B. and Popov, Alexey and Boltalina, Olga V. and Strauss, Steven H.},
abstractNote = {The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4F8I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4F8-containing rings, completely suppressing substitution on C(α) 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 Cupromoted (i) regiospecific perfluoroannulation, (ii) preparative C–F activation, and (iii) RD/A. HPLC-purified products were characterized by X-ray diffraction, low-temperature PES, and 1H/19F NMR.},
doi = {10.1002/chem.201504291},
journal = {Chemistry - A European Journal (Online)},
number = 3,
volume = 22,
place = {United States},
year = 2016,
month = 1
}
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