The First Applications of Carbene Ligands in Cross-Couplings of Alkyl Electrophiles: Sonogashira Reactions of Unactivated Alkyl Bromides and Iodides

Journal of the American Chemical Society

Volumn 125, Issue 45, 2003, Pages 13642-13643

  Eckhardt, Matthias ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; ANION; BROMIDE; CARBENE; HETEROCYCLIC COMPOUND; IODIDE; LIGAND; PALLADIUM; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; ELECTROPHILE; PROCESS OPTIMIZATION; SONOGASHIRA REACTION; STEREOCHEMISTRY;

ALKYNES; HYDROCARBONS, BROMINATED; HYDROCARBONS, IODINATED;

EID: 0242407300     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja038177r     Document Type: Article

References (29)

1. (a) Chemistry and Biology of Naturally-Occurring Acetylenes and Related Compounds; Lam, J., Breteler, H., Arnason, T., Hansen, L., Eds.; Elsevier: Amsterdam, 1988.
2. (b) Banthorpe, D. V. In Chemistry of Triple-Bonded Functional Groups; Patai, S., Ed.; Wiley: New York, 1994; pp 689-737.
3. (a) Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH: Weinheim, Germany, 1995.
4. (b) Chemistry of Triple-Bonded Functional Groups; Patai, S., Ed.; Wiley: New York, 1994.
5. (a) Sonogashira, K. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; Wiley-Interscience: New York, 2002; pp 493-529.
6. (b) Negishi, E.-i.; Anastasia, L. Chem. Rev. 2003, 103, 1979-2017.
7. (c) Tykwinski, R. R. Angew. Chem., Int. Ed. 2003, 42, 1566-1568.
8. Brandsma, L. Preparative Acetylenic Chemistry; Elsevier: Amsterdam, 1988.
9. (a) Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691-694.
10. (b) Netherton, M. R.; Dai, C.; Neuschütz, K.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 10099-10100.
11. (c) Kirchhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1945-1947.
12. (d) Netherton, M. R.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 3910-3912.
13. (e) Kirchhoff, J. H.; Netherton, M. R.; Hills, I. D.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 13662-13663.
14. (a) Devasagayaraj, A.; Stüdemann, T.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1995, 34, 2723-2725.
15. (b) Jensen, A. E.; Knochel, P. J. Org. Chem. 2002, 67, 79-85 and references therein.
16. (c) Zhou, J.; Fu, G. C. J. Am. Chem. Soc. 2003. In press.
17. (a) Terao, J.; Watanabe, H.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2002, 124, 4222-4223.
18. (b) Frisch, A. C.; Shaikh, N.; Zapf, A.; Beller, M. Angew. Chem., Int. Ed. 2002, 41, 4056-4059.
19. (c) Terao, J.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2003, 125, 5646-5647.
20. (a) Menzel, K.; Fu, G. C. J. Am. Chem. Soc. 2003, 125, 3718-3719.
21. (b) Tang, H.; Menzel, K.; Fu, G. C. Angew. Chem., Int. Ed. 2003. In press.
22. Lee, J.-Y.; Fu, G. C. J. Am. Chem. Soc. 2003, 125, 5616-5617.
23. For overviews of applications of N-heterocyclic carbene ligands in catalysis, see: (a) Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1290-1309.
24. (b) Hillier, A. C.; Grasa, G. A.; Viciu, M. S.; Lee, H. M.; Yang, C.; Nolan, S. P. J. Organomet. Chem. 2002, 653, 69-82.
25. For applications of Pd/N-heterocyclic carbene-based catalysts to Sonogashira reactions of aryl halides, see: (a) Herrmann, W. A.; Reisinger, C.-P.; Spiegler, M. J. Organomet. Chem. 1998, 557, 93-96.
26. (b) McGuinness, D. S.; Cavell, K. J. Organometallics 2000, 19, 741-748.
27. (c) Batey, R. A.; Shen, M.; Lough, A. J. Org. Lett. 2002, 4, 1411-1414.
28. 2 results in a modest yield of the desired product. AgI is ineffective.
29. (a) For Table 2, the olefin that is derived from the loss of HBr from the alkyl bromide is the predominant identifiable side product. (b) For Table 2, entries 12-14, at lower temperature or with less catalyst, more of the olefin side product is observed. (c) In preliminary experiments, reactions of (trimethylsilyl)acetylene and 5-hexynenitrile have also required a higher catalyst loading.