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Copper Causes Regiospecific Formation of C 4 F 8 ‐Containing Six‐Membered Rings and their Defluorination/Aromatization to C 4 F 4 ‐Containing Rings in Triphenylene/1,4‐C 4 F 8 I 2 Reactions
Author(s) -
Rippy Kerry C.,
Bukovsky Eric V.,
Clikeman Tyler T.,
Chen YuSheng,
Hou GaoLei,
Wang XueBin,
Popov Alexey A.,
Boltalina Olga V.,
Strauss Steven H.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504291
Subject(s) - aromatization , triphenylene , chemistry , copper , aromaticity , crystallography , ring (chemistry) , medicinal chemistry , stereochemistry , molecule , organic chemistry , catalysis
The presence of Cu in reactions of triphenylene (TRPH) and 1,4‐C 4 F 8 I 2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C 4 F 8 ‐containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive‐defluorination/aromatization (RD/A) to form C 4 F 4 ‐containing aromatic rings. Without Cu, the reactions of TRPH and 1,4‐C 4 F 8 I 2 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 1 H/ 19 F NMR.