Comparison of dppf-Supported Nickel Precatalysts for the Suzuki-Miyaura Reaction: The Observation and Activity of Nickel(I)

Ni‐based precatalysts for the Suzuki–Miyaura reaction have potential chemical and economic advantages compared to commonly used Pd systems. Here, we compare Ni precatalysts for the Suzuki–Miyaura reaction supported by the dppf ligand in 3 oxidation states, 0, I and II. Surprisingly, at 80 °C they gi...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2015-11, Vol.54 (45), p.13352-13356
Main Authors: Guard, Louise M., Mohadjer Beromi, Megan, Brudvig, Gary W., Hazari, Nilay, Vinyard, David J.
Format: Article
Language:English
Subjects:
Accessibility
Catalysis
Catalytic activity
Chemical reactions
cross-coupling
Economics
homogeneous catalysis
Joining
Ligands
Nickel
Organic chemistry
Oxidation
Phosphines
reaction mechanism
Substrates
Suzuki-Miyaura coupling
Valence
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Summary:Ni‐based precatalysts for the Suzuki–Miyaura reaction have potential chemical and economic advantages compared to commonly used Pd systems. Here, we compare Ni precatalysts for the Suzuki–Miyaura reaction supported by the dppf ligand in 3 oxidation states, 0, I and II. Surprisingly, at 80 °C they give similar catalytic activity, with all systems generating significant amounts of NiI during the reaction. At room temperature a readily accessible bench‐stable NiII precatalyst is highly active and can couple synthetically important heterocyclic substrates. Our work conclusively establishes that NiI species are relevant in reactions typically proposed to involve exclusively Ni0 and NiII complexes. I and only I: A series of Ni0, NiI and NiII complexes supported by a bidentate phosphine ligand were prepared. They are all active precatalysts for the Suzuki–Miyaura reaction, and generate an active NiI complex during catalysis. This observation led to the discovery of a bench‐stable NiII compound, which can couple heterocylic substrates at room temperature.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201505699