title: Palladium-Catalyzed Carbonylative α-Arylation of tert-Butyl Cyanoacetate with (Hetero)aryl Bromides.
abstract: A three-component coupling protocol has been developed for the generation of 3-oxo-3-(hetero)arylpropanenitriles via a carbonylative palladium-catalyzed α-arylation of tert-butyl 2-cyanoacetates with (hetero)aryl bromides followed by an acid-mediated decarboxylation step. Through the combination of only a stoichiometric loading of carbon monoxide and mild basic reaction conditions such as MgCl2 and dicyclohexylmethylamine for the deprotonation step, an excellent functional group tolerance was ensured for the methodology. Through the use of (13)C-labeled carbon monoxide generated from (13)COgen, the corresponding (13)C-isotopically labeled β-ketonitriles were obtained, and these products could subsequently be converted into cyanoalkynes and 3-cyanobenzofurans with site specific (13)C-isotope labeling.
authors.affiliation: Carbon Dioxide Activation Center (CADIAC), Department of Chemistry and the Interdisciplinary Nanoscience Center (iNANO), Aarhus University , Gustav Wieds Vej 14, 8000 Aarhus C, Denmark.
authors.forename: Mikkel T
authors.initials: MT
authors.lastname: Jensen
authors.affiliation: Carbon Dioxide Activation Center (CADIAC), Department of Chemistry and the Interdisciplinary Nanoscience Center (iNANO), Aarhus University , Gustav Wieds Vej 14, 8000 Aarhus C, Denmark.
authors.forename: Martin
authors.initials: M
authors.lastname: Juhl
authors.affiliation: Carbon Dioxide Activation Center (CADIAC), Department of Chemistry and the Interdisciplinary Nanoscience Center (iNANO), Aarhus University , Gustav Wieds Vej 14, 8000 Aarhus C, Denmark.
authors.forename: Dennis U
authors.initials: DU
authors.lastname: Nielsen
authors.affiliation: Process Research, H. Lundbeck A/S , Ottiliavej 9, 2500 Valby, Denmark.
authors.forename: Mikkel F
authors.initials: MF
authors.lastname: Jacobsen
authors.affiliation: Interdisciplinary Nanoscience Center (iNANO), Department of Engineering, Aarhus University , Finlandsgade 22, 8200 Aarhus N, Denmark.
authors.forename: Anders T
authors.initials: AT
authors.lastname: Lindhardt
authors.affiliation: Carbon Dioxide Activation Center (CADIAC), Department of Chemistry and the Interdisciplinary Nanoscience Center (iNANO), Aarhus University , Gustav Wieds Vej 14, 8000 Aarhus C, Denmark.
authors.forename: Troels
authors.initials: T
authors.lastname: Skrydstrup