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Aryl Triflates in On‐Surface Chemistry
Author(s) -
Ren Jindong,
Klaasen Henning,
Witteler Melanie C.,
Viergutz Lena,
Neugebauer Johannes,
Gao HongYing,
Studer Armido,
Fuchs Harald
Publication year - 2020
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.202002486
Subject(s) - regioselectivity , aryl , steric effects , chemistry , trifluoromethanesulfonate , sulfonyl , trifluoromethyl , aryl radical , reactivity (psychology) , molecule , photochemistry , hydrogen atom , monomer , coupling reaction , stereochemistry , group (periodic table) , organic chemistry , catalysis , medicine , alkyl , alternative medicine , polymer , pathology
The reactivity of aryl triflates in on‐surface C−C coupling is reported. It is shown that the triflate group in aryl triflates enables regioselective homo coupling with preceding or concomitant hydrodetriflation on Cu(111). Three different symmetrical π‐systems with two and three triflate functionalities were used as monomers leading to oligomeric conjugated π‐systems. The cascade, comprising different intermediates at different reaction temperatures as observed for one of the molecules, proceeds via initial removal of the trifluoromethyl sulfonyl group to give an aryloxy radical which in turn is deoxygenated to the corresponding aryl radical. Thermodynamically driven regioselective 1,2‐hydrogen atom transfer leads to a translocated aryl radical which in turn undergoes coupling. For a sterically more hindered bistriflate, where one ortho position was blocked, dehydrogenative coupling occurred at remote position with good regioselectivity. Starting materials, intermediates as well as products were analyzed by scanning tunneling microscopy. Structures and suggested mechanism were further supported by DFT calculations.