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Higher‐Order Zincates as Transmetalators in Alkyl–Alkyl Negishi Cross‐Coupling
Author(s) -
McCann Lucas C.,
Hunter Howard N.,
Clyburne Jason A. C.,
Organ Michael G.
Publication year - 2012
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201203547
Subject(s) - negishi coupling , alkyl , zincate , transmetalation , chemistry , solvent , coupling (piping) , salt (chemistry) , medicinal chemistry , polymer chemistry , organic chemistry , materials science , catalysis , metallurgy , zinc
Negishi revisited : Higher‐order alkyl zincates have been subjected to Negishi coupling with alkyl bromides. For the first time, coupling takes place in straight THF, i.e., without a salt additive and a high dielectric co‐solvent. This provides evidence that it is the higher‐order zincate that undergoes transmetalation to Pd, and not mono‐anionic zincates or any of the other species present in the Schlenk equilibrium.