Aryl Triflates in On‐Surface Chemistry

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 functional...

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Bibliographic Details
Published in:Chemistry : a European journal 2020-12, Vol.26 (70), p.16727-16732
Main Authors: Ren, Jindong, Klaasen, Henning, Witteler, Melanie C., Viergutz, Lena, Neugebauer, Johannes, Gao, Hong‐Ying, Studer, Armido, Fuchs, Harald
Format: Article
Language:English
Subjects:
Aromatic compounds
aryl triflate
Chemistry
Coupling
Coupling (molecular)
Dehydrogenation
Deoxygenation
homo coupling
Intermediates
Monomers
Regioselectivity
Scanning tunneling microscopy
self-assembly
STM
Surface chemistry
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Summary: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. Step aside! Coupling of aryl triflates, so far unknown in on‐surface chemistry, is reported. Unlike aryl halides known in Ullmann coupling, aryl radicals formed from triflated monomers undergo HAT prior to C−C coupling, leading to unexpected regioselectivity. But not only H‐atoms step aside: triflate fragments show a powerful templating effect during the reaction and leave the surface post‐synthetically under mild conditions.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202002486