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On the Radical Nature of Iron‐Catalyzed Cross‐Coupling Reactions
Author(s) -
Hedström Anna,
Izakian Zakieh,
Vreto Irma,
Wallentin CarlJohan,
Norrby PerOla
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406096
Subject(s) - halide , reagent , aryl , chemistry , alkyl , catalysis , quenching (fluorescence) , reductive elimination , coupling reaction , electron transfer , photochemistry , oxidative addition , substrate (aquarium) , combinatorial chemistry , fluorescence , organic chemistry , physics , oceanography , quantum mechanics , geology
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.