Boronic acids: New coupling partners in room-temperature Suzuki reactions of alkyl bromides. Crystallographic characterization of an oxidative-addition adduct generated under remarkably mild conditions

Journal of the American Chemical Society

Volumn 124, Issue 46, 2002, Pages 13662-13663

  Kirchhoff, Jan H ^a   Netherton, Matthew R ^a   Hills, Ivory D ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; BORONIC ACID DERIVATIVE; BROMINE DERIVATIVE;

ADDITION REACTION; ARTICLE; CHEMICAL REACTION; COMPLEX FORMATION; HYDROBORATION; OXIDATION; REACTION ANALYSIS; ROOM TEMPERATURE; X RAY CRYSTALLOGRAPHY;

BORONIC ACIDS; CATALYSIS; CHEMISTRY, ORGANIC; CRYSTALLOGRAPHY, X-RAY; HYDROCARBONS, BROMINATED; ORGANOMETALLIC COMPOUNDS; OXIDATION-REDUCTION; PALLADIUM;

EID: 0037146031     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0283899     Document Type: Article

References (28)

1. Correspondence concerning the X-ray crystal structure should be directed to I.D.H.
2. (a) Topics in Current Chemistry, Vol. 219; Miyaura, N., Ed.; Springer-Verlag: New York, 2002.
3. (b) Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: New York, 1998.
4. (a) Luh, T.-Y.; Leung, M.-K.; Wong, K.-T. Chem. Rev. 2000, 100, 3187-3204.
5. (b) Cárdenas, D. J. Angew. Chem., Int. Ed. 1999, 38, 3018-3020.
6. Palladium-catalyzed Suzuki couplings. (a) Alkyl iodides: Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691-694. (b) Alkyl bromides: Netherton, M. R.; Dai, C.; Neuschütz, K.; Fu, G. C. J. Am: Chem. Soc. 2001, 123, 10099-10100. (c) Alkyl chlorides: Kirchhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1945-1947. (d) Alkyl tosylates: Netherton, M. R.; Fu, G. C. Angew. Chem., Int. Ed., in press.
7. Palladium-catalyzed Suzuki couplings. (a) Alkyl iodides: Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691-694. (b) Alkyl bromides: Netherton, M. R.; Dai, C.; Neuschütz, K.; Fu, G. C. J. Am: Chem. Soc. 2001, 123, 10099-10100. (c) Alkyl chlorides: Kirchhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1945-1947. (d) Alkyl tosylates: Netherton, M. R.; Fu, G. C. Angew. Chem., Int. Ed., in press.
8. Palladium-catalyzed Suzuki couplings. (a) Alkyl iodides: Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691-694. (b) Alkyl bromides: Netherton, M. R.; Dai, C.; Neuschütz, K.; Fu, G. C. J. Am: Chem. Soc. 2001, 123, 10099-10100. (c) Alkyl chlorides: Kirchhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1945-1947. (d) Alkyl tosylates: Netherton, M. R.; Fu, G. C. Angew. Chem., Int. Ed., in press.
9. Palladium-catalyzed Suzuki couplings. (a) Alkyl iodides: Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691-694. (b) Alkyl bromides: Netherton, M. R.; Dai, C.; Neuschütz, K.; Fu, G. C. J. Am: Chem. Soc. 2001, 123, 10099-10100. (c) Alkyl chlorides: Kirchhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 1945-1947. (d) Alkyl tosylates: Netherton, M. R.; Fu, G. C. Angew. Chem., Int. Ed., in press.
10. Nickel-catalyzed Negishi couplings of alkyl bromides and iodides: Devasagayaraj, A.; Stüdemann, T.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1995, 34, 2723-2725. Jensen, A. E.; Knochel, P. J. Org. Chem. 2002, 67, 79-85, and references therein.
11. Nickel-catalyzed Negishi couplings of alkyl bromides and iodides: Devasagayaraj, A.; Stüdemann, T.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1995, 34, 2723-2725. Jensen, A. E.; Knochel, P. J. Org. Chem. 2002, 67, 79-85, and references therein.
12. Nickel-catalyzed Kumada couplings of alkyl bromides, chlorides, and tosylates: Terao, J.; Watanabe, H.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2002, 124, 4222-4223.
13. (a) Miyaura, N. Top. Curr. Chem. 2002, 219, 11-59.
14. (b) Suzuki, A. In Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: New York, 1998; Chapter 2.
15. For example, Frontier Scientific and Aldrich each sell more than 100 boronic acids.
16. We are aware of only one report of a Suzuki cross-coupling of a boronic acid with an alkyl electrophile that bears β hydrogens: Yang, G.-S.; Xie, X.-J.; Zhao, G.; Ding, Y. J. Fluorine Chem. 1999, 98, 159-161 (reactions of fluorinated alkyl iodides).
17. We decided to focus on tert-amyl alcohol, because the reaction components are more soluble in this solvent.
18. Strem Chemicals: catalog #15-1020.
19. 2.
20. In preliminary studies, heteroarylboronic acids, as well as certain electrondeficient arylboronic acids, have not proved to be suitable coupling partners.
21. 4 furnishes an 81-84% yield of the desired product, corresponding to a TON of ∼160. (c) We generally observe lower yields for reactions of more hindered substrates. To date, we have not achieved couplings of secondary alkyl bromides or secondary alkylboronic acids.
22. Strem Chemicals: catalog #15-1023.
23. For examples of the interchangeability of trialkylphosphines and their corresponding phosphonium salts in an array of processes, see: Netherton, M. R.; Fu, G. C. Org. Lett. 2001, 3, 4295-4298.
24. 2 reacts much more slowly (20% conversion after 20 h at room temperature) to exclusively generate the product of β-hydride elimination.
25. For a recent study of the oxidative addition of an aryl bromide to a Pd(0) complex at 25-70 °C, see: Stambuli, J. P.; Bühl, M.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 9346-9347.
26. Upon warming to 50 °C, complex 1 undergoes β-hydride elimination.
27. Adduct 1 also serves as a catalyst for the coupling of alkyl bromides with boronic acids at room temperature.
28. The conditions described in eq I are not suitable for Suzuki cross-couplings of boronic acids with alkyl chlorides.