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 language | English |
|---|---|
| Pages (from-to) | 922-936 |
| Number of pages | 15 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - Jan 18 2017 |
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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 journal › Article
}
TY - JOUR
T1 - Mechanistic study of an improved Ni precatalyst for Suzuki-Miyaura reactions of aryl sulfamates
T2 - Understanding the role of Ni(I) species
AU - Beromi, Megan Mohadjer
AU - Nova, Ainara
AU - Balcells, David
AU - Brasacchio, Ann M.
AU - Brudvig, Gary W
AU - Guard, Louise M.
AU - Hazari, Nilay
AU - Vinyard, David J.
PY - 2017/1/18
Y1 - 2017/1/18
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85018537542&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85018537542&partnerID=8YFLogxK
U2 - 10.1021/jacs.6b11412
DO - 10.1021/jacs.6b11412
M3 - Article
C2 - 28009513
AN - SCOPUS:85018537542
VL - 139
SP - 922
EP - 936
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 2
ER -