N-Arylations of Nitrogen-Containing Heterocycles with Aryl and Heteroaryl Halides Using a Copper(I) Oxide Nanoparticle/1,10-Phenanthroline Catalytic System

Abstract

A general procedure for solvent-free N-arylations of nitrogen-containing heterocycles, i.e. imidazoles, triazoles, and indoles, with aryl and heteroaryl halides catalyzed by copper(I) oxide (Cu₂O) nanoparticles is demonstrated. Four types of Cu₂O were evaluated: the bulky compound and its cubic, octahedral, and spherical nanoparticulate forms. The results show that Cu₂O nanoparticles, in particular the cubic form, are highly efficient for the N-arylation reaction. In the presence of cubic Cu₂O nanoparticles, 1,10-phenanthroline, and tetrabutylammonium fluoride, a variety of nitrogen-containing heterocycles smoothly underwent N-arylation with aryl and heteroaryl halides at 110-145 °C to give the corresponding products in moderate to excellent yields. It is noteworthy that the reaction is conducted under solvent-free conditions. The reaction mechanism is also discussed.

Key words

copper(I) oxide nanoparticles - 1,10-phenanthroline - N-arylations - heterocycles - halides

References

• For selected recent examples, see:
• 1a Zhong C. He J. Xue C. Li Y. Bioorg. Med. Chem.  2004,  12:  4009 
• 1b Dyck B. Goodfellow VS. Phillips T. Grey J. Haddach M. Rowbottom M. Naeve GS. Brown B. Saunders J. Bioorg. Med. Chem. Lett.  2004,  14:  1151 
• 1c Smallheer JM. Alexander RS. Wang J. Wang S. Nakajima S. Rossi KA. Smallwood A. Barbera F. Burdick D. Luettgen JM. Knabb RM. Wexler RR. Jadhav PK. Bioorg. Med. Chem. Lett.  2004,  14:  5263 
• 1d Qiao JX. Cheng X. Modi DP. Rossi KA. Luettgen JM. Knabb RM. Jadhav PK. Wexler RR. Bioorg. Med. Chem. Lett.  2005,  15:  29 
• 1e Mano T. Okumura Y. Sakakibara M. Okumura T. Tamura T. Miyamoto K. Stevens RW. J. Med. Chem.  2004,  47:  720 
• 1f Roppe J. Smith ND. Huang D. Tehrani L. Wang B. Anderson J. Brodkin J. Chung J. Jiang X. King C. Munoz B. Varney MA. Prasit P. Cosford NDP. J. Med. Chem.  2004,  47:  4645 
• 1g Venkatesan AM. Gu Y. Santos OD. Abe T. Agarwal A. Yang Y. Petersen PJ. Weiss WJ. Mansour TS. Nukaga M. Hujer AM. Bonomo RA. Knox JR. J. Med. Chem.  2004,  47:  6556 
• 1h Lange JHM. van Stuivenberg HH. Coolen HKAC. Adolfs TJP. McCreary AC. Keizer HG. Wals HC. Veerman W. Borst AJM. de Looff W. Verveer PC. Kruse CG. J. Med. Chem.  2005,  48:  1823 
• 1i Quan ML. Lam PYS. Han Q. Pinto DJP. He MY. Li R. Ellis CD. Clark CG. Teleha CA. Sun J.-H. Alexander RS. Bai S. Luettgen JM. Knabb RM. Wong PC. Wexler RR. J. Med. Chem.  2005,  48:  1729 
• 1j Barchéchath SD. Tawatao RI. Corr M. Carson DA. Cottam HB. J. Med. Chem.  2005,  48:  6409 
• 1k Voets M. Antes I. Scherer C. Müller-Vieira U. Biemel K. Barassin C. Marchais-Oberwinkler S. Hartmann RW. J. Med. Chem.  2005,  48:  6632 
• 1l Wiglenda T. Ott I. Kircher B. Schumacher P. Schuster D. Langer T. Gust R. J. Med. Chem.  2005,  48:  6516 
• 1m Jiang W. Guan J. Macielag MJ. Zhang S. Qiu Y. Kraft P. Bhattacharjee S. John TM. Haynes-Johnson D. Lundeen S. Sui Z. J. Med. Chem.  2005,  48:  2126 
• 1n Mahboobi S. Sellmer A. Hocher H. Eichhorn E. Bar T. Schmidt M. Maier T. Stadlwieser JF. Beckers TL. J. Med. Chem.  2006,  49:  5769 
• For selected papers on palladium-catalyzed N-arylations of imidazoles, see:
• 2a Hartwig JF. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley Interscience; New York: 2002.  p.1051 
• 2b Jiang L. Buchwald SL. In Metal-Catalyzed Cross-Coupling Reactions   de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004.  p.699 
• 2c Bellina F. Cauteruccio S. Mannina L. Rossi R. Viel S. J. Org. Chem.  2005,  70:  3997 
• For selected reviews on the use of copper as the catalyst, see:
• 3a Beletskaya IP. Cheprakov AV. Coord. Chem. Rev.  2004,  248:  2337 
• 3b Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 
• 4 For a paper on N-arylations of imidazoles with aryl halides mediated by stoichiometric copper, see: Lindley J. Tetrahedron  1984,  40:  1433 
• 5a Kiyomori A. Marcoux JF. Buchwald SL. Tetrahedron Lett.  1999,  40:  2657 
• 5b Kuil M. Bekedam EK. Visser GM. van den Hoogenband A. Terpstra JW. Kamer PCJ. Kamer van Leeuwen PWNM. van Strijdonck GPF. Tetrahedron Lett.  2005,  46:  2405 
• 5c Altman RA. Buchwald SL. Org. Lett.  2006,  8:  2779 
• 5d Altman RA. Koval ED. Buchwald SL. J. Org. Chem.  2007,  72:  6190 
• 5e Hosseinzadeh R. Tajbakhsh M. Alikarami M. Synlett  2006,  2124 
• 6a Klapars A. Antilla JC. Huang X. Buchwald SL. J. Am. Chem. Soc.  2001,  123:  7727 
• 6b Alcalde E. Dinarès I. Rodríguez S. Garcia de Miguel C. Eur. J. Org. Chem.  2005,  1637 
• 6c Antilla JC. Baskin JM. Barder TE. Buchwald SL. J. Org. Chem.  2004,  69:  5578 
• 7 Jerphagnon T. van Klink GPM. de Vries JG. van Koten G. Org. Lett.  2005,  7:  5241 
• 8a Ma D. Cai Q. Synlett  2004,  128 
• 8b Zhang H. Cai Q. Ma D. J. Org. Chem.  2005,  70:  5164 
• 8c Lv X. Wang Z. Bao W. Tetrahedron  2006,  62:  4756 
• 8d Deng W. Wang YF. Zhang C. Liu L. Guo QX. Chin. Chem. Lett.  2006,  17:  313 
• 9 Liu L. Frohn M. Xi N. Dominguez C. Hungate R. Reider PJ. J. Org. Chem.  2005,  70:  10135 
• 10 Rao H. Fu H. Jiang Y. Zhao Y. J. Org. Chem.  2005,  70:  8107 
• 11 Xu L. Zhu D. Wu F. Wang R. Wan B. Tetrahedron  2005,  61:  6553 
• 12a Zhang Z. Mao J. Zhu D. Wu F. Chen H. Wan B. Tetrahedron  2006,  62:  4435 
• 12b Yang M. Liu F. J. Org. Chem.  2007,  72:  8969 
• 13 Xie Y.-X. Pi S.-F. Wang J. Yin D.-L. Li J.-H. J. Org. Chem.  2006,  71:  8324 
• 14 Zhu L. Cheng L. Zhang Y. Xie R. You J. J. Org. Chem.  2007,  72:  2737 
• 15 Huang Y.-Z. Gao J. Ma H. Miao H. Xu J. Tetrahedron Lett.  2008,  49:  948 
• 16a Choudary BM. Sridhar C. Kantam ML. Venkanna GT. Sreedhar B. J. Am. Chem. Soc.  2005,  127:  9948 
• 16b Son SU. Park IK. Park J. Hyeon T. Chem. Commun.  2004,  778 
• 16c Taillefer M. Xia N. Ouali A. Angew. Chem. Int. Ed.  2007,  46:  934 
• 16d Kantam ML. Rao BPC. Choudary BM. Reddy RS. Synlett  2006,  2195 
• 16e Zhu L. Guo P. Li G. Lan J. Xie R. You J. J. Org. Chem.  2007,  72:  8535 
• For selected representative papers on copper-catalyzed N-arylations of imidazoles with other reagents, see:
• 17a Lopez-Alvarado P. Avendaño C. Menéndez JC. J. Org. Chem.  1995,  60:  5678 
• 17b Collman JP. Zhong M. Org. Lett.  2000,  2:  1233 
• 17c Collman JP. Zhong M. Zeng L. Costanzo S. J. Org. Chem.  2001,  66:  1528 
• 17d Collman JP. Zhong M. Zhang C. Costanzo S. J. Org. Chem.  2001,  66:  7892 
• 17e Lan J.-B. Chen L. Yu X.-Q. You J.-S. Xie R.-G. Chem. Commun.  2004,  188 
• 17f Lam PYS. Deudon S. Averill KM. Li R. He MY. DeShong P. Clark CG. J. Am. Chem. Soc.  2000,  122:  7600 
• 17g Fedorov AY. Finet J.-P. Tetrahedron Lett.  1999,  40:  2747 
• 17h Kang S.-K. Lee S.-H. Lee D. Synlett  2000,  1022 
• 17i Lam PYS. Clark CG. Saubern S. Adams J. Averill KM. Chan DMT. Combs A. Synlett  2000,  674 
• 17j Kantam ML. Venkanna GT. Sridhar C. Sreedhar B. Choudary BM. J. Org. Chem.  2006,  71:  9522 
• For selected papers on N-arylations of indoles using palladium, see:
• 18a Old DW. Harris MC. Buchwald SL. Org. Lett.  2000,  2:  1403 
• 18b Movassaghi M. Ondrus AE. J. Org. Chem.  2005,  70:  8638 
• Using copper, see:
• 18c Antilla JC. Klapars A. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  11684 
• 18d Chandrasekhar S. Sultana SS. Yaragorla SR. Reddy NR. Synthesis  2006,  839 
• 18e Zhou T. Chen Z.-C. Synth. Commun.  2002,  32:  903 
• 18f Bekolo H. Can. J. Chem.  2007,  85:  42 
• 19 Rout L. Jammi T. Punniyamurthy B.-X. Org. Lett.  2007,  9:  3397 
• 20 Tang B.-X. Wang F. Li J.-H. Xie Y.-X. Zhang MB. J. Org. Chem.  2007,  72:  6294 
• 21 For a paper on solvent-free, copper-catalyzed amination reactions of aryl halides with amines, see: Gajare AS. Toyota K. Yoshifuji M. Ozawa F. Chem. Commun.  2004,  1994 
• 22 Zhang S.-L. Liu L. Fu Y. Guo Q.-X. Organometallics  2007,  26:  4546 
• For representative papers on transition-metal-catalyzed cross-coupling reactions promoted by quaternary ammonium compounds, in particular TBAB, see:
• 23a Badone D. Baroni M. Cardamone R. Ielmini A. Guzzi U. J. Org. Chem.  1997,  62:  7170 
• 23b Bedford RB. Blake ME. Butts CP. Holder D. Chem. Commun.  2003,  466 
• 23c Lysén M. Köhler K. Synlett  2005,  1671 
• 23d Arvela RK. Leadbeater NE. Org. Lett.  2005,  7:  2101 
• 23e Liu W.-J. Xie Y.-X. Liang Y. Li J.-H. Synthesis  2006,  860 
• 24 Sundberg RJ. Mente DC. Yilmaz I. Gupta G. J. Heterocycl. Chem.  1977,  14:  1279 
• 25 Asproni B. Talani G. Busonero F. Pau A. Sanna S. Cerri R. Mascia MP. Sanna E. Biggio G. J. Med. Chem.  2005,  48:  2638 
• 26 Lampe JW. Di Meo SV. Traina JA. J. Heterocycl. Chem.  1994,  31:  287 
• 27 Lam PY. Clark CG. Sauber S. Adams J. Winters MP. Chan DM. Combs A. Tetrahedron Lett.  1998,  39:  2941 
• 28 Le Z.-G. Chen Z.-C. Hu Y. Zheng Q.-G. J. Chem. Res.  2004,  344 
• 29 Nonoyama M. Nakajima K. Polyhedron  1998,  18:  533