Nickel Catalyzed Carbonylative Cross Coupling for Direct Access to Isotopically Labeled Alkyl Aryl Ketones.

Autor: Mühlfenzl KS; Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark.; Early Chemical Development, Pharmaceutical Sciences, R&D, AstraZeneca, Gothenburg, Pepparedsleden 1, 43183, Mölndal, Sweden., Enemærke VJ; Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark., Gahlawat S; Department of Chemistry, UiT The Arctic University of Norway, Hansine Hansens veg 56, 9019, Tromsø.; Department of Chemistry, Hylleraas Center for Quantum Molecular Sciences, UiT The Arctic University of Norway, Hansine Hansens veg 56, 9019, Tromsø., Golbækdal PI; Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark., Munksgaard-Ottosen N; Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark., Neumann KT; Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark., Hopmann KH; Department of Chemistry, UiT The Arctic University of Norway, Hansine Hansens veg 56, 9019, Tromsø., Norrby PO; Data Science & Modelling, Pharmaceutical Sciences, R&D, AstraZeneca, Gothenburg, Pepparedsleden 1, 43183, Mölndal, Sweden., Elmore CS; Early Chemical Development, Pharmaceutical Sciences, R&D, AstraZeneca, Gothenburg, Pepparedsleden 1, 43183, Mölndal, Sweden., Skrydstrup T; Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 16; Vol. 63 (51), pp. e202412247. Date of Electronic Publication: 2024 Oct 17.
DOI: 10.1002/anie.202412247
Abstrakt: Here we present an effective nickel-catalyzed carbonylative cross-coupling for direct access to alkyl aryl ketones from readily accessible redox-activated tetrachlorophthalimide esters and aryl boronic acids. The methodology, which is run employing only 2.5 equivalents of CO and simple Ni(II) salts as the metal source, exhibits a broad substrate scope under mild conditions. Furthermore, this carbonylation chemistry provides an easy switch between isotopologues for stable ( 13 CO) and radioactive ( 14 CO) isotope labeling, allowing its adaptation to the late-stage isotope labeling of pharmaceutically relevant compounds. Based on DFT calculations as well as experimental evidence, a catalytic cycle is proposed involving a carbon-centered radical formed via nickel(I)-induced outer-sphere decarboxylative fragmentation of the redox-active ester.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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