Heterogenized Gold(I), Gold(III), and Palladium(II) Complexes for C-C Bond Reactions

Abstract

Recycling of heterogenized gold(I), gold(III), and palladium(II) complexes could be achieved for Suzuki and Sonogashira cross-coupling reaction between iodo benzene and arylboronic ­acids or alkynes. Au(I) and Pd(II) afford selectively nonsymmetrical biaryl compounds, while gold(III) complexes can only catalyze the arylboronic or alkynes homocoupling. Recycling occurs without loss of the catalytic activity after several reaction cycles.

Key words

C-C coupling - gold - Suzuki - Sonogashira - homogeneous catalysis - heterogenized

References and Notes

• 1a Hashmi ASK. Hutchings GJ. Angew. Chem. Int. Ed.  2006,  45:  7896 
• 1b Bond GC. Louis C. Thompson DT. In Catalysis by Gold   Imperial College Press; London: 2006. 
• 1c Dyker G. Angew. Chem. Int. Ed.  2000,  39:  4237 ; and references therein
• 2 Corma A. García H. Chem. Rev.  2003,  103:  4307 
• 3a Yao X. Li Ch.-J. J. Am. Chem. Soc.  2004,  126:  6884 
• 3b Wei Ch. Li Ch.-J. J. Am. Chem. Soc.  2003,  125:  9584 
• 4a Haruta M. Yamada N. Kobayashi T. Iijima S. J. Catal.  1989,  115:  301 
• 4b Guzman J. Gates BC. J. Am. Chem. Soc.  2004,  126:  2672 
• 4c Daniel MC. Astruc D. Chem. Rev.  2004,  104:  293 
• 4d Lemire C. Meyer R. Shaikhutdino S. Freund HJ. Angew. Chem. Int. Ed.  2004,  43:  118 
• 5 Corma A. Serna P. Science  2006,  313:  332 
• 6a Prati L. Rossi M. J. Catal.  1998,  176:  552 
• 6b Abad A. Concepción P. Corma A. García H. Angew. Chem. Int. Ed.  2005,  44:  4066 
• 6c Enache DI. Edwards JK. Landon P. Solsona-Espriu B. Carley AF. Herzing AA. Watanabe M. Kiely CJ. Knight DW. Hutchings GJ. Science  2006,  311:  362 
• 7a Carrettin S. Guzmán J. Corma A. Angew. Chem. Int. Ed.  2005,  44:  2242 
• 7b Hashmi ASK. Schwarz L. Choi J.-H. Frost TM. Angew. Chem. Int. Ed.  2000,  39:  2285 
• 8a Hashmi ASK. Angew. Chem. Int. Ed.  2005,  44:  6990 
• 8b Arcadi A. Di Giuseppe S. Curr. Org. Chem.  2004,  8:  795 
• 8c Hoffmann-Röder A. Krause N. Org. Biomol. Chem.  2005,  3:  387 
• 8d Hashmi ASK. Gold Bull.  2003,  36:  3 
• 8e Hashmi ASK. Gold Bull.  2004,  37:  51 
• 8f González-Arellano C. Corma A. Iglesias M. Sánchez F. Chem. Commun.  2005,  3451 
• 8g Hashmi ASK. Salatte R. Frey W. Chem. Eur. J.  2006,  12:  6991 
• 8h Hashmi ASK. Weyrauch JP. Rudolph M. Kurpejovic E. Angew. Chem. Int. Ed.  2004,  43:  6545 
• 9a Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PG. Wiley-VCH; Weinheim: 1997. 
• 9b Transition Metals for Organic Synthesis, Building Blocks and Fine Chemicals   Beller M. Wiley-VCH; Weinheim: 2004. 
• 10a Kresge CT. Leonowicz ME. Roth WJ. Vartuli JC. Beck JS. Nature (London)  1992,  359:  710 
• 10b Beck JS. Roth WJ. Leonowicz ME. Kresge CT. Schmitt KD. Chu CT.-W. Olson KH. Sheppard E. McCullen SB. Higgins JB. Schlenk JL. J. Am. Chem. Soc.  1992,  114:  10834 
• 11a Corma A. Fornés V. Pergher SB. Nature (London)  1998,  396:  353 
• 11b Corma A. Fornés V. Martínez-Triguero J. Pergher SB. J. Catal.  1999,  186:  57 
• 11c Corma A. Fornés V. Guil JM. Pergher SB. Maesen ThLM. Buglass JG. Microporous Mesoporous Mater.  2000,  38:  301 
• 12a González-Arellano C. Gutiérrez-Puebla E. Iglesias M. Sánchez F. Eur. J. Inorg. Chem.  2004,  1955 
• 12b Corma A. Gutiérrez-Puebla E. Iglesias M. Monge A. Pérez-Ferreras S. Sánchez F. Adv. Synth. Catal.  2006,  348:  1899 

13

Suzuki: the reaction was carried out in a 25 mL vessel, at 130 °C in a time range of 3-24 h. In a typical run, a mixture of aryl halide (10 mmol), boronic acid (15 mmol), aq K₃PO₄ (20 mmol), and catalyst (10-20 mol%) in 3 mL of o-xylene was stirred for the desired time. The solution was allowed to cool, and a 1:1 mixture of Et₂O-H₂O (20 mL) was added. The organic layer was washed, separated, further washed with another 10 mL portion of Et₂O, dried with anhyd MgSO₄, and filtered. The solvent and volatiles were completely removed under vacuum to give the crude product which subjected to column chromatographic separation resulted in pure compounds. The reaction was followed by GC-MS. At the end of the process, the mixture of reaction was filtered; the residue of support-containing catalyst washed to completely remove the remains of products and/or reactants and used again.

14

Sonogashira: The reaction was carried out in a 25 mL vessel, at 130 °C during 24 h. In a typical run, a mixture of aryl halide (10 mmol), alkyne (15 mmol), aq K₂CO₃ or K₃PO₄ (20 mmol) and catalyst (10-20 mol%) in 3 mL of o-xylene was stirred for the desired time. The reaction was followed by GC-MS. At the end of the process, the mixture of reaction was filtered; the residue of support-containing catalyst washed to completely remove the remains of products and/or reactants, and used again.