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Synlett 2005(10): 1624-1626  
DOI: 10.1055/s-2005-869854
LETTER
© Georg Thieme Verlag Stuttgart · New York

Highly Efficient Nickel-Catalyzed Heck Reaction Using Ni(acac)2/N-Heterocyclic Carbene Catalyst

Kiyofumi Inamoto*, Jun-ichi Kuroda, Tomohiro Danjo, Takao Sakamoto
Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3, Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, Japan
Fax: +81(22)7956864; e-Mail: inamoto@mail.pharm.tohoku.ac.jp;
Further Information

Publication History

Received 18 April 2005
Publication Date:
07 June 2005 (online)

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Abstract

Ni(acac)2/N-heterocyclic carbene-derived catalysts were shown to be highly efficient in the nickel-catalyzed Heck reaction. Various aryl halides were reacted with acrylate to give the coupled products in good to high yield.

Key words

nickel - carbene ligands - Heck reaction - catalysis

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  • 11a

    Other nickel sources such as NiCl2 and Ni(OAc)2 were ineffective.

  • 11b

    Reactions in toluene, dioxane, NMP, and DMA proceeded in relatively poor yields.

12

Use of Ag2CO3, t-BuOK, CsF, CsOAc, or Et3N rather than Cs2CO3, K2CO3 or Na2CO3, led to a decreased yield. In addition, after the catalyst optimization (Table 1), it was found that the use of Na2CO3 gave similar but slightly better results than Cs2CO3 in almost all cases (Table 2).

13

Reactions of aryl bromides in the absence of Bu4NI resulted in poorer yields. However, the role of such an ammonium salt is obscure at present.

14

Under the optimized conditions we developed here, we have not yet obtained the products in satisfactory yields from the reaction of aryl chlorides.