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Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis
journal contribution
posted on 2020-06-03, 19:35 authored by Andrew
L. Clevenger, Ryan M. Stolley, Justis Aderibigbe, Janis LouieA critically important
process in catalysis is the formation of
an active catalyst from the combination of a metal precursor and a
ligand, as the efficacy of this reaction governs the amount of active
catalyst. This Review is a comprehensive overview of reactions catalyzed
by nickel and an added bidentate phosphine, focusing on the steps
transforming the combination of precatalyst and ligand into an active
catalyst and the potential effects of this transformation on nickel
catalysis. Reactions covered include common cross-coupling reactions,
such as Suzuki, Heck, Kumada, and Negishi couplings, addition reactions,
cycloadditions, C–H functionalizations, polymerizations, hydrogenations,
and reductive couplings, among others. Overall, the most widely used
nickel precatalyst with free bidentate phosphines is Ni(cod)2, which accounts for ∼50% of the reports surveyed,
distantly followed by Ni(acac)2 and Ni(OAc)2, which account for ∼10% each. By compiling the reports
of these reactions, we have calculated statistics of the usage and
efficacy of each ligand with Ni(cod)2 and other nickel
sources. The most common bidentate phosphines are simple, relatively
inexpensive ligands, such as DPPE, DCPE, DPPP, and DPPB, along with
others with more complex backbones, such as DPPF and Xantphos. The
use of expensive chiral phosphines is more scattered, but the most
common ligands include BINAP, Me-Duphos, Josiphos, and related analogs.