New Cobalt-Catalyzed Cross-Coupling Reactions of Heterocyclic Chlorides with Aryl and Heteroaryl Magnesium Halides

Abstract

New cobalt-catalyzed cross-coupling between arylmagnesium halides and 2-chloropyridines and related heterocycles occur at low temperature leading to 2-arylated heterocycles in good yields.

cobalt-catalysis - cross-coupling - organomagnesium reagents - arylation - heterocycles

References

1a Diederich F. Stang PJ. Metal-Catalyzed Cross-Coupling Reactions   Wiley-VCH; Weinheim: 1998. 

1b Miyaura N. Cross-Coupling Reactions. A Practical Guide   Springer; Berlin: 2002. 

2 Li JJ. Gribble GW. Palladium in Heterocyclic Synthesis   Vol. 20:  Tetrahedron Organic Chemistry Series, Pergamon; Amsterdam: 2000. 

For excellent reviews of palladium cross-coupling reactions, see:

3a Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 

3b Whitcombe NJ. Hii KK. Gibson SE. Tetrahedron  2001,  57:  7449 

3c Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 

3d Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 

4a Li GY. Marshall WJ. Organometallics  2002,  21:  590 

4b Wu J. Yang Z. J. Org. Chem.  2001,  66:  7875 

4c Srogl J. Liu W. Marshall D. Liebeskind LS. J. Am. Chem. Soc.  1999,  121:  9949 

4d Erdelmeier I. Gais HJ. J. Am. Chem. Soc.  1989,  111:  1125 

4e Tasler S. Lipshutz BH. J. Org. Chem.  2003,  68:  1190 

4f Lipshutz BH. Blomgren PA. J. Am. Chem. Soc.  1999,  121:  5819 

4g Kiso Y. Tamao K. Kumada M. J. Organomet. Chem.  1973,  50:  C 12 

5a Fürstner A. Leitner A. Méndez M. Krause H. J. Am. Chem. Soc.  2002,  124:  13856 

5b Quintin J. Frank X. Hocquemiller R. Figadère B. Tetrahedron Lett.  2002,  43:  3547 

5c Tamura M. Kochi JK. J. Am. Chem. Soc.  1971,  93:  1487 

5d Tamura M. Kochi JK. Synthesis  1971,  303 

5e Neumann SM. Kochi JK. J. Org. Chem.  1975,  40:  599 

5f Smith RS. Kochi JK. J. Org. Chem.  1976,  41:  502 

5g Kochi JK. Acc. Chem. Res.  1974,  7:  351 

6a Cahiez G. Avedissian H. Synthesis  1998,  1199 

6b Cahiez G. Marquais S. Pure Appl. Chem.  1996,  68:  53 

6c Dohle W. Kopp F. Cahiez G. Knochel P. Synlett  2001,  1901 

6d Molander GA. Rahn BJ. Shubert DC. Bonde SE. Tetrahedron Lett.  1983,  24:  5449 

7a Hodgson DM. Witherington J. Moloney BA. Richards LC. Brayer J.-L. Synlett  1995,  32 

7b Le Gall E. Gosmini C. Nedelec J.-Y. Périchon J. Tetrahedron Lett.  2001,  42:  267 

7c Gomes P. Fillon H. Gosmini C. Labbé E. Périchon J. Tetrahedron  2002,  58:  8417 

8a Cahiez G. Avedissian H. Tetrahedron Lett.  1998,  39:  6159 

8b Avedissian H. Bérillon L. Cahiez G. Knochel P. Tetrahedron Lett.  1998,  39:  6163 

For palladium catalyzed cross-coupling reactions using 2-halopyridines and related derivatives, see:

9a Trécourt F. Gervais B. Mallet M. Quéguiner G. J. Org. Chem.  1996,  61:  1673 

9b Turck A. Plé N. Leprêtre-Gaquère A. Quéguiner G. Heterocycles  1998,  49:  205 

9c Bonnet V. Mongin F. Trécourt F. Quéguiner G. Knochel P. Tetrahedron Lett.  2001,  42:  5717 

9d Gros P. Fort Y. Synthesis  1999,  754 

9e Savage SA. Smith AP. Fraser CL. J. Org. Chem.  1998,  63:  10048 

9f Fang Y.-Q. Hanan GS. Synlett  2003,  852 

For the preparation of functionalized arylmagnesium compounds, see:

10a Boymond L. Rottländer M. Cahiez G. Knochel P. Angew. Chem. Int. Ed.  1998,  37:  1701 

10b Varchi G. Kofink C. Lindsay DM. Ricci A. Knochel P. Chem. Commun.  2003,  396 

10c Sapountzis I. Knochel P. Angew. Chem. Int. Ed.  2002,  41:  1610 

11

Commercially cobalt powder was used (Aldrich, 99.9+% purity).

12

Commercially iron powder was used (Merck, 99.5% purity).