January 18, 2016
Journal Article

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(ß) atoms to form C4F8-containing rings, completely suppressing substitution on C(a) 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.

Revised: March 17, 2016 | Published: January 18, 2016

Citation

Rippy K.C., E.V. Bukovsky, T.T. Clikeman, Y. Chen, G. Hou, X.B. Wang, and A. Popov, et al. 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. Chemistry - A European Journal 22, no. 3:874-877. PNNL-SA-111662. doi:10.1002/chem.201504291