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Inhibition of (dppf)nickel-catalysed Suzuki–Miyaura cross-coupling reactions by α-halo-N-heterocycles† † Electronic supplementary information (ESI) available: Characterisation data for new compounds; data from kinetic studies; data and coordinates from computational chemistry studies. CCDC 2103814, 2103815, 2103816 and 2103817. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/d1sc04582b

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. Nickel complexes with a dppf ligand can form inactive dinickel(ii) complexes during Suzuki–Miyaura cross-coupling reactions. However, these complexes can react with Grignard reagents in Kumada–Tamao–Corriu cross-coupling reactions.

SUBMITTER: Cooper A

PROVIDER: S-EPMC8565371 | biostudies-literature |

REPOSITORIES: biostudies-literature

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