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300072 (China) [ + + ]D iese Autoren haben zu gleichen Teilen zu der Arbeit beigetragen. Hintergrundinformationen und die Identifikationsnummern (OR-CIDs) der Autoren sind unter: https://doi.org/10.1002/ange.202011858 zu finden. 2020 Die Autoren. AngewandteChemie verçffentlichtv on Wiley-VCH GmbH. Dieser Open Access Beitrag steht unter den Bedingungen der Creative Commons AttributionN on-CommercialN o-Derivs License, die eine Nutzung und Verbreitung in allen Medien gestattet, sofern der ursprüngliche Beitrag ordnungsgemäßzitiert und nicht fürkommerzielle Zwecke genutzt wird und keine ¾nderungen und Anpassungen vorgenommenwerden.

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.