title: Copper Causes Regiospecific Formation of C4 F8 -Containing Six-Membered Rings and their Defluorination/Aromatization to C4 F4 -Containing Rings in Triphenylene/1,4-C4 F8 I2 Reactions.
abstract: The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4 F8 I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4 F8 -containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive-defluorination/aromatization (RD/A) to form C4 F4 -containing aromatic rings. Without Cu, the reactions of TRPH and 1,4-C4 F8 I2 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.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA.
authors.forename: Kerry C
authors.initials: KC
authors.lastname: Rippy
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA.
authors.forename: Eric V
authors.initials: EV
authors.lastname: Bukovsky
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA.
authors.forename: Tyler T
authors.initials: TT
authors.lastname: Clikeman
authors.affiliation: ChemMatCARS, University of Chicago Advanced Proton Source, Argonne, IL, 60439, USA.
authors.forename: Yu-Sheng
authors.initials: YS
authors.lastname: Chen
authors.affiliation: Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352, USA.
authors.forename: Gao-Lei
authors.initials: GL
authors.lastname: Hou
authors.affiliation: Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352, USA. xuebin.wang@pnnl.gov.
authors.forename: Xue-Bin
authors.initials: XB
authors.lastname: Wang
authors.affiliation: Leibniz Institute for Solid State and Materials Research, 01069, Dresden, Germany. a.popov@ifw-dresden.de.
authors.forename: Alexey A
authors.identifier: http://orcid.org/0000-0002-7596-0378
authors.initials: AA
authors.lastname: Popov
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA. olga.boltalina@colostate.edu.
authors.forename: Olga V
authors.initials: OV
authors.lastname: Boltalina
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA. steven.strauss@colostate.edu.
authors.forename: Steven H
authors.identifier: http://orcid.org/0000-0001-7636-2671
authors.initials: SH
authors.lastname: Strauss
keywords: X-ray structure; aromatization; copper; perfluoroalkylation; triphenylene