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Low Temperature Studies of Iron‐Catalyzed Cross‐Coupling of Alkyl Grignard Reagents with Aryl Electrophiles
Author(s) -
Kleimark Jonatan,
Larsson PerFredrik,
Emamy Parisa,
Hedström Anna,
Norrby PerOla
Publication year - 2012
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201100392
Subject(s) - chemistry , reagent , aryl , electrophile , catalysis , alkyl , coupling (piping) , catalytic cycle , reductive elimination , coupling reaction , inorganic chemistry , photochemistry , medicinal chemistry , organic chemistry , metallurgy , materials science
Abstract The title reaction has been studied under low temperature conditions. Coupling with active substrates can be done even at dry ice temperature. Initial rate studies at −25 °C indicate that high concentrations of any reagent can lead to either complete or partial catalyst deactivation. Under strongly reducing conditions, iron seems to form less active complexes that only slowly re‐enter the catalytic cycle, possibly through bimolecular coupling of iron(II) complexes. Computational studies support the experimental observations, and indicate that oxidation states below +I cannot be reached by reductive elimination.