Cross-Couplings of Unactivated Secondary Alkyl Halides: Room-Temperature Nickel-Catalyzed Negishi Reactions of Alkyl Bromides and Iodides

Journal of the American Chemical Society

Volumn 125, Issue 48, 2003, Pages 14726-14727

  Zhou, Jianrong ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; BROMIDE; HALIDE; IODIDE; LIGAND; NICKEL;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL PARAMETERS; CHEMICAL REACTION; ROOM TEMPERATURE;

HYDROCARBONS, BROMINATED; HYDROCARBONS, IODINATED; NICKEL; ORGANOMETALLIC COMPOUNDS; PALLADIUM; TEMPERATURE;

EID: 0344861888     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0389366     Document Type: Article

References (27)

1. For reviews of metal-catalyzed cross-coupling reactions, see: (a) Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: New York, 1998.
2. (b) Cross-Coupling Reactions: A Practical Guide; Miyaura, N., Ed.; Topics in Current Chemistry Series 219; Springer-Verlag: New York 2002.
3. (c) Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; Wiley-Interscience: New York, 2002.
4. 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.
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.
6. 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.
7. Suzuki cross-couplings: (a) Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691-694.
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12. Negishi cross-couplings: (a) Devasagayaraj, A.; Stüdemann, T.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1995, 34, 2723-2725.
13. (b) Giovannini, R.; Stüdemann, T.; Dussin, G.; Knochel, P. Angew. Chem., Int. Ed. 1998, 37, 2387-2390.
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18. Kumada cross-couplings: (a) Terao, J.; Watanabe, H.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2002, 124, 4222-4223.
19. (b) Terao, J.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2003, 125, 5646-5647.
20. For a recent example of a stoichiometric coupling of a secondary alkylnickel with an arylzinc reagent, see: O'Brien, E. M.; Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2003, 125, 10498-10499.
21. (a) Organozinc Reagents, A Practical Approach; Knochel, P., Jones, P., Eds.; Oxford: New York, 1999.
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23. (c) Boudier, A.; Bromm, L. O.; Lotz, M.; Knochel, P. Angew. Chem., Int. Ed. 2000, 39, 4414-4435.
24. (d) Hou, S. Org. Lett. 2003, 5. 423-425.
25. We observe essentially no n-dodecane (<0.5%), indicating that the isopropylnickel complex is not undergoing β-hydride elimination to generate an n-propylnickel complex.
26. We speculate that the chelating nature of Pybox ligands may disfavor β-hydride elimination, which requires a vacant coordination site.
27. Notes: (a) The standard coupling conditions can also be applied to Negishi reactions of activated alkyl halides. For example, n-nonylZnBr couples with allyl bromide, benzyl bromide, and benzyl chloride in 60, 89, and 100% yields (by GC, versus a calibrated intemal standard), respectively. (b) The use of secondary organozinc reagents leads to lower yields (<30%). (c) Alkyl chlorides, alkyl tosylates, and tertiary alkyl bromides/iodides are not suitable coupling partners under the standard conditions.