Mechanistic study of an improved Ni precatalyst for Suzuki-Miyaura reactions of aryl sulfamates

Understanding the role of Ni(I) species

Megan Mohadjer Beromi, Ainara Nova, David Balcells, Ann M. Brasacchio, Gary W Brudvig, Louise M. Guard, Nilay Hazari, David J. Vinyard

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Nickel precatalysts are potentially a more sustainable alternative to traditional palladium precatalysts for the Suzuki-Miyaura coupling reaction. Currently, there is significant interest in Suzuki-Miyaura coupling reactions involving readily accessible phenolic derivatives such as aryl sulfamates, as the sulfamate moiety can act as a directing group for the prefunctionalization of the aromatic backbone of the electrophile prior to cross-coupling. By evaluating complexes in the Ni(0), (I), and (II) oxidation states we report a precatalyst, (dppf)Ni(σ-tolyl)(Cl) (dppf = 1,1'-bis(diphenylphosphino)-ferrocene), for Suzuki-Miyaura coupling reactions involving aryl sulfamates and boronic acids, which operates at a significantly lower catalyst loading and at milder reaction conditions than other reported systems. In some cases it can even function at room temperature. Mechanistic studies on precatalyst activation and the speciation of nickel during catalysis reveal that Ni(I) species are formed in the catalytic reaction via two different pathways: (i) the precatalyst (dppf)Ni(σ-tolyl)(Cl) undergoes comproportionation with the active Ni(0) species; and (ii) the catalytic intermediate (dppf)Ni(Ar) (sulfamate) (Ar = aryl) undergoes comproportionation with the active Ni(0) species. In both cases the formation of Ni(I) is detrimental to catalysis, which is proposed to proceed via a Ni(0)/Ni(II) cycle. DFT calculations are used to support experimental observations and provide insight about the elementary steps involved in reactions directly on the catalytic cycle, as well as off-cycle processes. Our mechanistic investigation provides guidelines for designing even more active nickel catalysts.

Original languageEnglish
Pages (from-to)922-936
Number of pages15
JournalJournal of the American Chemical Society
Volume139
Issue number2
DOIs
Publication statusPublished - Jan 18 2017

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Nickel
Catalysis
Catalysts
Boronic Acids
Discrete Fourier transforms
Palladium
Chemical activation
Derivatives
Oxidation
Acids
Guidelines
Temperature
sulfamic acid

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Mechanistic study of an improved Ni precatalyst for Suzuki-Miyaura reactions of aryl sulfamates : Understanding the role of Ni(I) species. / Beromi, Megan Mohadjer; Nova, Ainara; Balcells, David; Brasacchio, Ann M.; Brudvig, Gary W; Guard, Louise M.; Hazari, Nilay; Vinyard, David J.

In: Journal of the American Chemical Society, Vol. 139, No. 2, 18.01.2017, p. 922-936.

Research output: Contribution to journalArticle

Beromi, Megan Mohadjer ; Nova, Ainara ; Balcells, David ; Brasacchio, Ann M. ; Brudvig, Gary W ; Guard, Louise M. ; Hazari, Nilay ; Vinyard, David J. / Mechanistic study of an improved Ni precatalyst for Suzuki-Miyaura reactions of aryl sulfamates : Understanding the role of Ni(I) species. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 2. pp. 922-936.
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