Journal
ACS CATALYSIS
Volume 12, Issue 3, Pages 1905-1918Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c05586
Keywords
catalysis; cobalt; cross-coupling; Suzuki-Miyaura; phenoxyimine
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Funding
- National Institutes of Health [5R01GM121441]
- Bristol Myers Squibb through the Princeton Catalysis Initiative
- Natural Sciences and Engineering Research Council of Canada
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In this study, efficient precatalysts for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross-coupling reaction between alkyl bromides and neopentylglycol (hetero)arylboronic esters were generated in situ using Cobalt(II) halides in combination with phenoxyimine (FI) ligands. The protocol allowed for efficient C-C bond formation with various nucleophiles and electrophiles. The results also suggested that alkyl radicals play an important role in the catalytic reaction.
Cobalt(II) halides in combination with phenoxyimine (FI) ligands generated efficient precatalysts in situ for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross-coupling between alkyl bromides and neopentylglycol (hetero)arylboronic esters. The protocol enabled efficient C-C bond formation with a host of nucleophiles and electrophiles (36 examples, 34-95%) with precatalyst loadings of 5 mol %. Studies with alkyl halide electrophiles that function as radical clocks support the intermediacy of alkyl radicals during the course of the catalytic reaction. The improved performance of the FI-cobalt catalyst was correlated with decreased lifetimes of cage-escaped radicals as compared to those of diamine-type ligands. Studies of the phenoxyimine-cobalt coordination chemistry validate the L,X interaction leading to the discovery of an optimal, well-defined, air-stable mono-FI-cobalt(II) precatalyst structure.
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