Mild and Efficient Nickel-Catalyzed Heck Reactions with Electron-Rich Olefins

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  • Thomas Gøgsig, Denmark
  • Jonatan Kleimark, University Gothenburg, Dept Chem, SE-41296 Gothenburg, Sweden
  • Sten O. Nilsson Lill, University Gothenburg, Dept Chem, SE-41296 Gothenburg, Sweden
  • Signe Korsager, Denmark
  • Anders Thyboe Lindhardt, Denmark
  • Per-Ola Norrby, University of Gothenburg, Sweden
  • Troels Skrydstrup
A new efficient protocol for the nickel-catalyzed Heck reaction of aryl triflates with vinyl ethers is presented. Mild reaction conditions that equal those of the corresponding palladium-catalyzed Heck reaction are applied, representing a practical and more sustainable alternative to the conventional regioselective arylation of vinyl ethers. A catalytic system comprised of Ni(COD)2 and 1,1′-bis(diphenylphosphino)ferrocene (DPPF) in combination with the tertiary amine Cy2NMe proved effective in the olefination of a wide range of aryl triflates. Both electron-deficient and electron-rich arenes proved compatible, and the corresponding aryl methyl ketone could be secured after hydrolysis in yields approaching quantitative. Good functional group tolerance was observed matching the characteristics of the analogous Pd-catalyzed Heck reaction. The high levels of catalytic activity were explained by the intermediacy of a cationic nickel(II) complex potentially responsible for the successive β-hydride elimination and base promoted catalyst regeneration. Although these elementary reactions are normally considered challenging, DFT calculations suggested this pathway to be favorable under the applied reaction conditions.
Original languageEnglish
JournalJournal of the American Chemical Society
Volume134
Issue1
Pages (from-to)443-452
Number of pages10
ISSN0002-7863
DOIs
Publication statusPublished - 11 Jan 2012

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