Moegling Julian, Hoffmann Alexander, Thomas Fabian, Orth Nicole, Liebhäuser Patricia, Herber Ulrich, Rampmaier Robert, Stanek Julia, Fink Gerhard, Ivanović-Burmazović Ivana, Herres-Pawlis Sonja
Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Department Chemie und Pharmazie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, 91058, Erlangen, Germany.
Angew Chem Int Ed Engl. 2018 Jul 16;57(29):9154-9159. doi: 10.1002/anie.201713171. Epub 2018 Jun 19.
Heteroscorpionate ligands of the bis(pyrazolyl)methane family have been applied in the stabilisation of terminal copper tosyl nitrenes. These species are highly active intermediates in the copper-catalysed direct C-H amination and nitrene transfer. Novel perfluoroalkyl-pyrazolyl- and pyridinyl-containing ligands were synthesized to coordinate to a reactive copper nitrene centre. Four distinct copper tosyl nitrenes were prepared at low temperatures by the reaction with SO tBuPhINTs and copper(I) acetonitrile complexes. Their stoichiometric reactivity has been elucidated regarding the imination of phosphines and the aziridination of styrenes. The formation and thermal decay of the copper nitrenes were investigated by UV/Vis spectroscopy of the highly coloured species. Additionally, the compounds were studied by cryo-UHR-ESI mass spectrometry and DFT calculations. In addition, a mild catalytic procedure has been developed where the copper nitrene precursors enable the C-H amination of cyclohexane and toluene and the aziridination of styrenes.
双（吡唑基）甲烷家族的异蝎形配体已被应用于稳定末端对甲苯磺酰基氮烯铜。这些物种是铜催化直接C-H胺化和氮烯转移中高度活跃的中间体。合成了新型含全氟烷基-吡唑基和吡啶基的配体，以与反应性铜氮烯中心配位。通过与SO tBuPhINTs和铜（I）乙腈配合物反应，在低温下制备了四种不同的对甲苯磺酰基氮烯铜。关于膦的亚胺化和苯乙烯的氮杂环丙烷化，已经阐明了它们的化学计量反应性。通过对高度显色物种的紫外/可见光谱研究了铜氮烯的形成和热衰减。此外，还通过低温超高压电喷雾电离质谱和密度泛函理论计算对这些化合物进行了研究。此外，还开发了一种温和的催化方法，其中铜氮烯前体能够实现环己烷和甲苯的C-H胺化以及苯乙烯的氮杂环丙烷化。
