Copper-catalyzed domino halide exchange-cyanation of aryl bromides

Journal of the American Chemical Society

Volumn 125, Issue 10, 2003, Pages 2890-2891

  Zanon, Jacopo ^a   Klapars, Artis ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BROMIDE; COPPER; CYANIDE; DIAMINE; HALIDE; IODIDE; LIGAND; PALLADIUM;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; TEMPERATURE;

CATALYSIS; COPPER; CYANIDES; HYDROCARBONS, AROMATIC; HYDROCARBONS, BROMINATED;

EID: 0037433554     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0299708     Document Type: Article

References (27)

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2. (a) Rosenmund, K. W.; Struck, E. Chem. Ber. 1919, 52, 1749. (b) Pongratz, A. Monatsh. Chem. 1927, 48, 585. (c) von Braun, J.; Manz, G. Liebigs Ann. Chem. 1931, 488, 111. (d) Connor, J. A.; Leeming, S. W.; Price, R. J. Chem. Soc., Perkin Trans. 1 1990, 1127. (e) Carr, R. M.; Cable, K. M.; Wells, G. N.; Sutherland, D. R. J. Labelled Compd. Radiopharm. 1994, 34, 887. A single example of Cu-catalyzed (5 mol % CuI) cyanation of an aryl bromide has been reported to proceed with 55% conversion when the reaction is carried out in an ionic liquid: (f) Wu, J. X.; Beck, B.; Ren, R. X. Tetrahedron Lett. 2002, 43, 387.
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23. Conversion of 5-iodo-m-xylene into 3,5-dimethylbenzonitrile (in the absence of added KI) was performed using 10 mol % Cu precatalyst, 1.0 equiv of ligand 1, and 1.2 equiv of NaCN in toluene for 24 h at 90 °C. All three precatalysts (CuI, CuBr, CuCN) afforded 96-98% yield (GC) and 99.7-99.9% conversion of aryl iodide.
24. Conversion of 5-bromo-m-xylene into 3,5-dimethylbenzonitrile using 10 mol % Cu precatalyst, 1.0 equiv of ligand 1, and 1.2 equiv of NaCN in toluene for 24 h at 110 °C provided the following yields of the nitrile product: CuI, 82%; CuBr, 2%; CuCN, 1%.
25. The copper-catalyzed cyanation reactions are sensitive to oxygen and moisture. Nevertheless, glovebox techniques are not required (see Supporting Information).
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