meta-C-H Arylation of Aniline Derivatives via Palladium/ S,O-Ligand/Norbornene Cooperative Catalysis.

Autor: Sukowski V; Van't Hoff Institute for Molecular Sciences, Science Park 904, 1098 XH, Amsterdam, The Netherlands., van Borselen M; Van't Hoff Institute for Molecular Sciences, Science Park 904, 1098 XH, Amsterdam, The Netherlands., Mathew S; Van't Hoff Institute for Molecular Sciences, Science Park 904, 1098 XH, Amsterdam, The Netherlands., de Bruin B; Van't Hoff Institute for Molecular Sciences, Science Park 904, 1098 XH, Amsterdam, The Netherlands., Fernández-Ibáñez MÁ; Van't Hoff Institute for Molecular Sciences, Science Park 904, 1098 XH, Amsterdam, The Netherlands.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jan 25; Vol. 63 (5), pp. e202317741. Date of Electronic Publication: 2023 Dec 22.
DOI: 10.1002/anie.202317741
Abstrakt: Aromatic amines are ubiquitous moieties in organic molecules and their direct functionalization is of great interest in many research areas due to their prevalence in pharmaceuticals and organic electronics. While several synthetic tools exist for the ortho- and para-functionalization of anilines, the functionalization of the less reactive meta-position is not easy to achieve with current methods. To date, the meta-C-H arylation of aniline derivatives has been restricted to either the use of directing groups & templates, or their transformation into anilides & quaternary anilinium salts. Herein, we report the first general and efficient meta-C-H-arylation of non-directed aniline derivatives via cooperative catalysis with a palladium-S,O-ligand-norbornene system. The reaction proceeds under mild conditions with a wide range of aniline derivatives and aryl iodides, while being operationally simple and scalable. Our preliminary mechanistic investigation-including the isolation of several palladium complexes and deuterium experiments-reveal useful insights into the substituent-effects of both the aniline-substrate and the norbornene-mediator during the meta-C-H activation step.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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