Cross-Couplings of Alkyl Electrophiles under "Ligandless" Conditions: Negishi Reactions of Organozirconium Reagents

Journal of the American Chemical Society

Volumn 126, Issue 1, 2004, Pages 82-83

  Wiskur, Sheryl L ^a   Korte, Alexander ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; HALIDE; LIGAND; ORGANOZIRCONIUM DERIVATIVE; PALLADIUM COMPLEX; REAGENT; TOLUENESULFONIC ACID DERIVATIVE; UNCLASSIFIED DRUG; ZIRCONIUM DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL REACTION; CROSS COUPLING REACTION; ELECTROCHEMISTRY; NEGISHI REACTION;

EID: 0347760049     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0393729     Document Type: Article

References (38)

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5. sp3-X electrophiles, see: Cárdenas, D. J. Angew. Chem., Int. Ed. 2003, 42, 384-387. Cárdenas, D. J. Angew. Chem., Int. Ed. 1999, 38, 3018-3020. See also: Luh, T.-Y.; Leung, M.-k.; Wong, K.-T. Chem. Rev. 2000, 100, 3187-3204.
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26. By "ligandless", we are simply indicating that typical ligands such as phosphines are not present. For a discussion of other ligandless catalysts for cross-coupling reactions, see: Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; pp 26, 208, 214, 233.
27. For reviews of the zirconium-Negishi reaction, see: (a) Negishi, E.-i. In Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; pp 1-47.
28. (b) Negishi, E.-i. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; Wiley-Interscience: New York, 2002: pp 229-247.
29. For an example of a natural-product synthesis that employs a zirconium-Negishi reaction, see: Ribe, S.; Kondru, R. K.; Beratan, D. N.; Wipf, P. J. Am. Chem. Soc. 2000. 122, 4608-4617.
30. Notes: (a) The cross-coupling proceeds efficiently in NMP alone, but not in THF.
31. (b) Under otherwise identical conditions, if the alkenyl-zirconium reagent is replaced with nonylzinc bromide, we observe essentially no cross-coupling (<2%).
32. (c) In addition to zirconium-Negishi reactions of primary alkyl electrophiles, these conditions are also effective for couplings of aryl bromides (but not aryl chlorides).
33. Under these conditions, secondary alkyl bromides are not suitable substrates.
34. 2Br.
35. 2-catalyzed reactions appear to be homogeneous. For an excellent discussion, including leading references, of approaches to distinguishing between homogeneous and heterogeneous catalysis, see: Widegren, J. A.; Bennett, M. A.; Finke, R. G. J. Am. Chem. Soc. 2003, 125, 10301-10310.
36. 2-catalyzed reactions appear to be homogeneous. For an excellent discussion, including leading references, of approaches to distinguishing between homogeneous and heterogeneous catalysis, see: Widegren, J. A.; Bennett, M. A.; Finke, R. G. J. Am. Chem. Soc. 2003, 125, 10301-10310.
37. (b) For an example of a coupling catalyzed by palladium nanoparticles, see: Reetz, M. T.; Westermann, E. Angew. Chem., Int. Ed. 2000, 39, 165-168.
38. The cross-coupling proceeds in the presence of radical traps.