Reusable Cu₂O-Nanoparticle-Catalyzed Amidation of Aryl Iodides

Abstract

The amidation of aryl iodides using Cu₂O nanoparticles is described. It is a heterogeneous process, no leaching of the Cu₂O species occurs, and the catalyst can be recovered and recycled without loss of activity.

Cu₂O nanoparticles - heterogeneous catalysis - cross-coupling reaction - amide - aryl iodide

References and Notes

1a Beletskaya IP. Cheprakov AV. Coord. Chem. Rev.  2004,  248:  2337 

1b Hartwig JF. Synlett  2006,  1283 

1c Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 

1d Corbet J.-P. Mignani G. Chem. Rev.  2006,  106:  2651 

1e Evano G. Blanchard N. Toumi M. Chem. Rev.  2008,  108:  3054 

1f Kondo T. Mitsudo T.-A. Chem. Rev.  2000,  100:  3205 

2a Voets M. Antes I. Scherer C. Muller-Vieira U. Biemel K. Barassin C. Marchais-Oberwinkler S. Hartmann RW. J. Med. Chem.  2005,  48:  6632 

2b Quan ML. Lam PYS. Han Q. Pinto DJP. He MY. Li R. Ellis CD. Clark CG. Teleha CA. Sun JH. Alexander RS. Bai S. Luettgen JM. Knabb RM. Wong PC. Wexler RR. J. Med. Chem.  2005,  48:  1729 

2c De Martino G. Edler MC. La Regina G. Colsuccia A. Barbera MC. Barrow D. Nicholson RI. Chiosis G. Brancale A. Hamel E. Artico M. Silvestri R. J. Med. Chem.  2006,  49:  947 

2d Kadlor SW. Kalish VJ. Davies JF. Shetty BV. Fritz JE. Appelt K. Burgess JA. Campanale KM. Chirgadze NY. Clawson DK. Dressman BA. Hatch SD. Khalil DA. Kosa MB. Lubbehusen PP. Muesing MA. Patick AK. Reich SH. Su KS. Tatlock JH. J. Med. Chem.  1997,  40:  3979 

3 Goldberg I. Ber. Dtsch. Chem. Ges.  1906,  39:  1691 

For some examples, see:

4a Yin J. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  6043 

4b Huang X. Anderson KW. Zim D. Jiang L. Klapars A. Buchwald SL. J. Am. Chem. Soc.  2003,  125:  6653 

4c Shen Q. Hartwig JF. J. Am. Chem. Soc.  2007,  129:  7734 

4d Ikawa T. Barder TE. Biscoe MR. Buchwald SL. J. Am. Chem. Soc.  2007,  129:  13001 

4e Yin J. Buchwald SL. Org. Lett.  2000,  2:  1101 

4f Hartwig JF. Kawatsura M. Hauck SI. Shaughnessy KH. Alcazar-Roman LM.
J. Org. Chem.  1999,  64:  5575 

4g Ghosh A. Sieser JE. Riou M. Cai W. Rivera-Ruiz L. Org. Lett.  2003,  5:  2207 

4h Manley PJ. Bilodeau MT. Org. Lett.  2004,  6:  2433 

4i Shen Q. Shekhar S. Stambuli JP. Hartwig JF. Angew. Chem. Int. Ed.  2005,  44:  1371 

4j Klapars A. Campos KR. Chen C.-Y. Volante RP. Org. Lett.  2005,  7:  1185 

For some examples, see:

5a Klapars A. Antilla JC. Huang X. Buchwald SL. J. Am. Chem. Soc.  2001,  123:  7727 

5b Strieter ER. Blackmond DG. Buchwald SL. J. Am. Chem. Soc.  2005,  127:  4120 

5c Pan X. Cai Q. Ma D. Org. Lett.  2004,  6:  1809 

5d Klapars A. Huang X. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  7421 

5e Mallesham B. Rajesh BM. Reddy PR. Srinivas D. Trehan S. Org. Lett.  2003,  5:  963 

5f Hosseinzadeh R. Tajbakhsh M. Mohadjerani M. Mehdinejad H. Synlett  2004,  1517 

5g Guo X. Rao H. Fu H. Jiang Y. Zhao Y. Adv. Synth. Catal.  2006,  348:  2197 

5h Lv X. Bao W. J. Org. Chem.  2007,  72:  3863 

For some examples, see:

6a Deng W. Wang Y.-F. Zou Y. Liu L. Guo Q.-X. Tetrahedron Lett.  2004,  45:  2311 

6b Chen Y.-J. Chen H.-H. Org. Lett.  2006,  8:  5609 

6c Soares do Rêgo Barros O. Nogueira CW. Stangherlin EC. Menezes PH. Zeni G. J. Org. Chem.  2006,  71:  1552 

6d Cristau H.-J. Cellier PP. Spindler J.-F. Taillefer M. Chem. Eur. J.  2004,  10:  5607 

6e Chandrasekhar S. Sultana SS. Yaragorla SR. Reddy NR. Synthesis  2006,  839 

6f Moriwaki K. Satoh K. Takada M. Ishino Y. Ohno T. Tetrahedron Lett.  2005,  46:  7559 

6g Strieter ER. Bhayana B. Buchwald SL.
J. Am. Chem. Soc.  2009,  131:  78 

6h Mino T. Harada Y. Shindo H. Sakamoto M. Fujita T. Synlett  2008,  614 

6i Zhu L. Cheng L. Zhang Y. Xie R. You J. J. Org. Chem.  2007,  72:  2737 

For some examples, see:

7a Rout L. Sen TK. Punniyamurthy T. Angew. Chem. Int. Ed.  2007,  46:  5583 

7b Rout L. Jammi S. Punniyamurthy T. Org. Lett.  2007,  9:  3397 

7c Jammi S. Sakthivel S. Rout L. Mukherjee T. Mandal S. Mitra R. Saha P. Punniyamurthy T.
J. Org. Chem.  2009,  74:  1971 

7d Zhang J. Zhang Z. Wang Y. Zheng X. Wang Z. Eur. J. Org. Chem.  2008,  5112 

7e Li J.-H. Tang B.-X. Tao L.-M. Xie Y.-X. Liang Y. Zhang M.-B. J. Org. Chem.  2006,  71:  7488 

7f Tang B.-X. Wang F. Li J.-H. Xie Y.-X. Zhang M.-B. J. Org. Chem.  2007,  72:  6294 

8a Wu W.-T. Wang Y. Shi L. Pang W. Zhu Q. Xu G. Lu F. J. Phys. Chem. B  2006,  110:  14702 

8b Gou L. Murphy CJ. Nano Lett.  2003,  3:  231 

9a Liu L. Zhang Y. Wang Y. J. Org. Chem.  2005,  70:  6122 

9b Reed NN. Dickerson TJ. Boldt GE. Janda KD. J. Org. Chem.  2005,  70:  1728 

9c Chandrasekhar S. Narsihmulu Ch. Sultana SS. Reddy NR. Org. Lett.  2002,  4:  4399 

9d Svennebring A. Garg N. Nilsson P. Hallberg A. Larhed M. J. Org. Chem.  2005,  70:  4720 

9e Wang L. Zhang Y. Liu L. Wang Y. J. Org. Chem.  2006,  71:  1284 

10

General Procedure for Amidation of Aryl Iodides
Aryl iodide (1 mmol), amide (1.2 mmol), and CuI (10 mol%) were stirred at 120 ˚C in the presence of KOH (1 mmol) in PEG₄₀₀₀ (1 g) under N₂ atmosphere. Progress of the reaction was monitored by TLC. After completion, the reaction flask was cooled to r.t., and the reaction mixture was treated with EtOAc (10 mL). The resulting solution was washed with H₂O (3 × 2 mL). Drying (Na₂SO₄) and evaporation of the solvent gave a residue that was purified on a short pad of silica gel using hexane and EtOAc as eluent. All the isolated products were characterized by IR, ^¹H NMR, and ^¹³C NMR spectroscopy, and elemental analysis. Recyclability Experiment 1-Iodo-4-methylbenzene (5 mmol), benzamide (6 mmol), and CuI (10 mol%) were stirred at 120 ˚C in the presence of KOH (7.5 mmol) in PEG₄₀₀₀ (5 g) under N₂ atmosphere. After the reaction, the reaction material was treated with EtOAc (10 mL) and H₂O (5 mL). The aqueous layer having the Cu₂O nanoparticles were centrifuged, and the precipitate was washed with deionized H₂O (3 ¥ 2 mL) and acetone (3 ¥ 2 mL). After drying in vacuum, the Cu₂O nanoparticles were reused for the fresh reaction of benzamide with 1-iodo-4-methylbenzene.