Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles

Alasdair K. Cooper; Megan E. Greaves; William Donohoe; Paul M. Burton; Thomas O. Ronson; Alan R. Kennedy; David J. Nelson

doi:10.1039/D1SC04582B

Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles

Alasdair K. Cooper, Megan E. Greaves, William Donohoe, Paul M. Burton, Thomas O. Ronson, Alan R. Kennedy, David J. Nelson

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

58 Downloads (Pure)

Abstract

A nickel/dppf catalyst system was found to successfully achieve the Suzuki-Miyaura cross-coupling reactions of 3- and 4-chloropyridine and of 6-chloroquinoline but not of 2-chloropyridine or of other α-halo-N-heterocycles. Further investigations revealed that chloropyridines undergo rapid oxidative addition to [Ni(COD)(dppf)] but that α-halo-N-heterocycles lead to the formation of stable dimeric nickel species that are catalytically inactive in Suzuki-Miyaura cross-coupling reactions. However, the corresponding Kumada-Tamao-Corriu reactions all proceed readily, which is attributed to more rapid transmetalation of Grignard reagents.

Original language	English
Pages (from-to)	14074-14082
Number of pages	9
Journal	Chemical Science
Volume	12
Issue number	42
Early online date	11 Oct 2021
DOIs	https://doi.org/10.1039/D1SC04582B
Publication status	Published - 14 Nov 2021

Keywords

nickel/dppf catalyst
Suzuki-Miyaura reaction
cross-coupling reactions

Access to Document

10.1039/D1SC04582BLicence: CC BY 3.0

Cooper-etal-CS-2021-Inhibition-of-dppf-nickel-catalysed-Suziki-MiyauraFinal published version, 1.23 MBLicence: CC BY 3.0

Computational Screening Of Nickel Complexes For The Activation Of `Inert? Bonds
Nelson, D. (Principal Investigator)
Carnegie Trust for the Universities of Scotland
1/01/19 → 1/01/20
Project: Research
AstraZeneca ICASE
Nelson, D. (Principal Investigator)
Astra Zeneca
1/10/17 → 30/09/21
Project: Research - Studentship
Industrial CASE Account - University of Strathclyde 2017 | Greaves, Megan
Nelson, D. (Principal Investigator), Murphy, J. (Co-investigator) & Greaves, M. (Research Co-investigator)
EPSRC (Engineering and Physical Sciences Research Council)
1/10/17 → 14/09/21
Project: Research Studentship Case - Internally allocated

Data for: "Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles"
Cooper, A. (Creator), Greaves, M. (Creator), Donohoe, W. (Creator) & Nelson, D. (Creator), University of Strathclyde, 14 Oct 2021
DOI: 10.15129/a7c7ed8e-bb39-4632-8716-39d43c872264
Dataset

ARCHIE-WeSt (UOSHPC)
Martin, R. (Manager)
University Of Strathclyde
Facility/equipment: Facility
AVII+600 NMR Spectrometer
Parkinson, J.
Pure And Applied Chemistry
Facility/equipment: Equipment
AVIII400 NMR Spectrometer with Cryoprobe
Parkinson, J.
Pure And Applied Chemistry
Facility/equipment: Equipment

Cite this

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title = "Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles",

abstract = "A nickel/dppf catalyst system was found to successfully achieve the Suzuki-Miyaura cross-coupling reactions of 3- and 4-chloropyridine and of 6-chloroquinoline but not of 2-chloropyridine or of other α-halo-N-heterocycles. Further investigations revealed that chloropyridines undergo rapid oxidative addition to [Ni(COD)(dppf)] but that α-halo-N-heterocycles lead to the formation of stable dimeric nickel species that are catalytically inactive in Suzuki-Miyaura cross-coupling reactions. However, the corresponding Kumada-Tamao-Corriu reactions all proceed readily, which is attributed to more rapid transmetalation of Grignard reagents.",

keywords = "nickel/dppf catalyst, Suzuki-Miyaura reaction, cross-coupling reactions",

author = "Cooper, {Alasdair K.} and Greaves, {Megan E.} and William Donohoe and Burton, {Paul M.} and Ronson, {Thomas O.} and Kennedy, {Alan R.} and Nelson, {David J.}",

year = "2021",

month = nov,

day = "14",

doi = "10.1039/D1SC04582B",

language = "English",

volume = "12",

pages = "14074--14082",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles

AU - Cooper, Alasdair K.

AU - Greaves, Megan E.

AU - Donohoe, William

AU - Burton, Paul M.

AU - Ronson, Thomas O.

AU - Kennedy, Alan R.

AU - Nelson, David J.

PY - 2021/11/14

Y1 - 2021/11/14

N2 - A nickel/dppf catalyst system was found to successfully achieve the Suzuki-Miyaura cross-coupling reactions of 3- and 4-chloropyridine and of 6-chloroquinoline but not of 2-chloropyridine or of other α-halo-N-heterocycles. Further investigations revealed that chloropyridines undergo rapid oxidative addition to [Ni(COD)(dppf)] but that α-halo-N-heterocycles lead to the formation of stable dimeric nickel species that are catalytically inactive in Suzuki-Miyaura cross-coupling reactions. However, the corresponding Kumada-Tamao-Corriu reactions all proceed readily, which is attributed to more rapid transmetalation of Grignard reagents.

AB - A nickel/dppf catalyst system was found to successfully achieve the Suzuki-Miyaura cross-coupling reactions of 3- and 4-chloropyridine and of 6-chloroquinoline but not of 2-chloropyridine or of other α-halo-N-heterocycles. Further investigations revealed that chloropyridines undergo rapid oxidative addition to [Ni(COD)(dppf)] but that α-halo-N-heterocycles lead to the formation of stable dimeric nickel species that are catalytically inactive in Suzuki-Miyaura cross-coupling reactions. However, the corresponding Kumada-Tamao-Corriu reactions all proceed readily, which is attributed to more rapid transmetalation of Grignard reagents.

KW - nickel/dppf catalyst

KW - Suzuki-Miyaura reaction

KW - cross-coupling reactions

U2 - 10.1039/D1SC04582B

DO - 10.1039/D1SC04582B

M3 - Article

SN - 2041-6520

VL - 12

SP - 14074

EP - 14082

JO - Chemical Science

JF - Chemical Science

IS - 42

ER -

Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles

Abstract

Keywords

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Projects

Computational Screening Of Nickel Complexes For The Activation Of `Inert? Bonds

AstraZeneca ICASE

Industrial CASE Account - University of Strathclyde 2017 | Greaves, Megan

Datasets

Data for: "Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles"

Equipment

ARCHIE-WeSt (UOSHPC)

AVII+600 NMR Spectrometer

AVIII400 NMR Spectrometer with Cryoprobe

Cite this