Rh(I)-catalyzed direct arylation of pyridines and quinolines

Journal of the American Chemical Society

Volumn 130, Issue 45, 2008, Pages 14926-14927

  Berman, Ashley M ^a   Lewis, Jared C ^a   Bergman, Robert G ^a   Ellman, Jonathan A ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BROMIDE; PYRIDINE DERIVATIVE; QUINOLINE DERIVATIVE; RHENIUM;

ARTICLE; ARYLATION; CATALYSIS; CHEMICAL STRUCTURE; ELECTRON;

BENZENE DERIVATIVES; CATALYSIS; PYRIDINES; QUINOLINES; RHODIUM;

EID: 57349094283     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8059396     Document Type: Article

References (17)

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2. Billingsley, K. L.; Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47, 4695.
3. For a recent comprehensive review on direct arylation, see: Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 2007, 107, 174.
4. Excess Zn and catalytic Pd/C have been used to prepare 2-phenylpyridine in 52% yield from pyridine and phenyl chloride: Mukhopadhyay, S.; Rothenberg, G.; Gitis, D.; Baidossi, M.; Ponde, D. E.; Sasson, Y. Perkin Trans. 2 2000, 9, 1809.
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7. (c) Cho, S. H.; Hwang, S. J.; Chang, S. J. Am. Chem. Soc. 2008, 130, 9254.
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10. For Ni- and Lewis acid-catalyzed C-2 alkenylation of pyridines with alkynes, see: Nakao, Y.; Kanyiva, K. S.; Hiyama, T. J. Am. Chem. Soc. 2008, 130, 2448.
11. The direct arylation of azoles proceeds most efficiently with Rh(I) salts containing alkene rather than CO ligands and requires the addition of either an electron-rich trialkylphosphine or a phosphepine, see: Lewis, J. C.; Berman, A. M.; Bergman, R. G.; Ellman, J. A. J. Am. Chem. Soc. 2008, 130, 2493.
12. 2 in a different type of C-H bond functionalization reaction, see: Zhao, X.; Yu, Z. J. Am. Chem. Soc. 2008, 130, 8136.
13. The role of excess heterocycle may be to both stabilize the Rh catalyst and act as an acid scavenger.
14. Mass balance experiments indicate <10% unproductive loss of the heterocycle after complete consumption of the aryl bromide. For all of the aryl bromides investigated, neither hydrodehalogenation nor dimerization was observed.
15. For relevant studies on the impact of pyridyl C-2 substitution on C-H bond activation, see the following. (a) Iridium complexes: Alvarez, E.; Conejero, S.; Paneque, M.; Petronilho, A.; Poveda, M. L.; del Rio, D.; Serrano, O.; Carmona, E. J. Am. Chem. Soc. 2006, 128, 13060.
16. (b) Osmium complexes: Buil, M. L.; Esteruelas, M. A.; Garcés, K.; Oliván, M.; Oñate, E. J. Am. Chem. Soc. 2007, 129, 10998.
17. For several mechanistic possibilities, please see the Supporting Information.