title: On the radical nature of iron-catalyzed cross-coupling reactions.
abstract: The radical nature of iron-catalyzed cross-coupling between Grignard reagents and alkyl halides has been studied by using a combination of competitive kinetic experiments and DFT calculations. In contrast to the corresponding coupling with aryl halides, which commences through a classical two-electron oxidative addition/reductive elimination sequence, the presented data suggest that alkyl halides react through an atom-transfer-initiated radical pathway. Furthermore, a general iodine-based quenching methodology was developed to enable the determination of highly accurate concentrations of Grignard reagents, a capability that facilitates and increases the information output of kinetic investigations based on these substrates.
authors.affiliation: Department of Chemistry and Molecular Biology, Gothenburg University, Kemivägen 10, 41296 Gothenburg (Sweden).
authors.forename: Anna
authors.initials: A
authors.lastname: Hedström
authors.forename: Zakieh
authors.initials: Z
authors.lastname: Izakian
authors.forename: Irma
authors.initials: I
authors.lastname: Vreto
authors.forename: Carl-Johan
authors.initials: CJ
authors.lastname: Wallentin
authors.forename: Per-Ola
authors.initials: PO
authors.lastname: Norrby
mesh_terms: D000478:Alkylation; D001555:Benzene Derivatives / Q000737:chemistry; D001965:Bromides / Q000737:chemistry*; D002384:Catalysis; D007202:Indicators and Reagents; D007501:Iron / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D001555:Benzene Derivatives; D001965:Bromides; D007202:Indicators and Reagents; D007501:Iron
keywords: Grignard reaction; atom transfer; cross-coupling; iron; radical reactions