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Mild and efficient nickel-catalyzed Heck reactions with electron-rich olefins.
J Am Chem Soc 2012; 134(1):443-52JA

Abstract

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 Cy(2)NMe 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.

Authors+Show Affiliations

The Center for Insoluble Protein Structures (inSPIN), Department of Chemistry and the Interdisciplinary Nanoscience Center, Aarhus University, Langelandsgade 140, 8000 Aarhus, Denmark.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

22126421

Citation

Gøgsig, Thomas M., et al. "Mild and Efficient Nickel-catalyzed Heck Reactions With Electron-rich Olefins." Journal of the American Chemical Society, vol. 134, no. 1, 2012, pp. 443-52.
Gøgsig TM, Kleimark J, Lill SO, et al. Mild and efficient nickel-catalyzed Heck reactions with electron-rich olefins. J Am Chem Soc. 2012;134(1):443-52.
Gøgsig, T. M., Kleimark, J., Lill, S. O., Korsager, S., Lindhardt, A. T., Norrby, P. O., & Skrydstrup, T. (2012). Mild and efficient nickel-catalyzed Heck reactions with electron-rich olefins. Journal of the American Chemical Society, 134(1), pp. 443-52. doi:10.1021/ja2084509.
Gøgsig TM, et al. Mild and Efficient Nickel-catalyzed Heck Reactions With Electron-rich Olefins. J Am Chem Soc. 2012 Jan 11;134(1):443-52. PubMed PMID: 22126421.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Mild and efficient nickel-catalyzed Heck reactions with electron-rich olefins. AU - Gøgsig,Thomas M, AU - Kleimark,Jonatan, AU - Lill,Sten O Nilsson, AU - Korsager,Signe, AU - Lindhardt,Anders T, AU - Norrby,Per-Ola, AU - Skrydstrup,Troels, Y1 - 2011/12/22/ PY - 2011/12/1/entrez PY - 2011/12/1/pubmed PY - 2012/5/9/medline SP - 443 EP - 52 JF - Journal of the American Chemical Society JO - J. Am. Chem. Soc. VL - 134 IS - 1 N2 - 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 Cy(2)NMe 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. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/22126421/Mild_and_efficient_nickel_catalyzed_Heck_reactions_with_electron_rich_olefins_ L2 - https://dx.doi.org/10.1021/ja2084509 DB - PRIME DP - Unbound Medicine ER -