Direct Access to Isotopically Labeled Aliphatic Ketones Mediated by Nickel(I) Activation. (2nd March 2020)

• Record Type: Journal Article
• Authors: Donslund, Aske S.; Pedersen, Simon S.; Gaardbo, Cecilie; Neumann, Karoline T.; Kingston, Lee; Elmore, Charles S.; Skrydstrup, Troels
• Is Part Of: Angewandte Chemie. Volume 132:Number 21(2020)
• Page Start: 8176
• Page End: 8180
• Publication Date: 2020-03-02
• Subjects: Carbonylierung -- Isotopenmarkierung -- Ketone -- Ligandeneffekte -- Nickel; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201916391
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: An extensive range of functionalized aliphatic ketones with good functional‐group tolerance has been prepared by a Ni I ‐promoted coupling of either primary or secondary alkyl iodides with NN2 pincer Ni II ‐acyl complexes. The latter were easily accessed from the corresponding Ni II ‐alkyl complexes with stoichiometric CO. This Ni‐mediated carbonylative coupling is adaptable to late‐stage carbon isotope labeling, as illustrated by the preparation of isotopically labelled pharmaceuticals. Preliminary investigations suggest the intermediacy of carbon‐centered radicals. Abstract : Ideal zum Markieren : Ni I ‐Komplexe können die carbonylierende Kupplung von Ni II ‐Acyl‐Komplexen mit primären und sekundären Iodiden vermitteln; dies bietet eine allgemeine Methode zur Synthese aliphatischer Ketone direkt aus CO. Die Methode ist ideal für die Kohlenstoffisotopenmarkierung, wie anhand des Zugangs zu biologisch aktiven, 13 C‐ und 14 C‐haltigen Molekülen illustriert wird.