Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2017; 28(10): 1177-1182
DOI: 10.1055/s-0036-1588741
DOI: 10.1055/s-0036-1588741
letter
Copper Oxide Nanoparticles as a Mild and Efficient Catalyst for N-Arylation of Imidazole and Aniline with Boronic Acids at Room Temperature
Further Information
Publication History
Received: 02 February 2017
Accepted after revision: 14 February 2017
Publication Date:
09 March 2017 (online)
Abstract
The present work describes the excellent catalytic activity of copper(II) oxide nanoparticles (NPs) towards N-arylation of aniline and imidazole at room temperature. The copper(II)oxide NPs were synthesized by a thermal refluxing technique and characterized by FT-IR spectroscopy; powder XRD, SEM, EDX, TEM, TGA, XPS, BET surface area analysis, and particle size analysis. The size of the NPs was found to be around 12 nm having a surface area of 164.180 m2 g–1.The catalytic system was also found to be recyclable and could be reused in subsequent catalytic runs without a significant loss of activity.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588741.
- Supporting Information
-
References and Notes
- 1a Yudin AK, Hartwig JF. Catalyzed Carbon-Heteroatom Bond Formation. Wiley-VCH; Weinheim: 2010
- 1b Monnier F, Taillefer M. Angew. Chem. Int. Ed. 2009; 48: 6954-6954
- 1c Hartwig JF. Nature (London, U.K.) 2008; 455: 314-314
- 1d Buchwald SL. Acc. Chem. Res. 2008; 41: 1439-1439
- 1e Surry DS, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 6338-6338
- 1f Evano G, Blanchard N, Toumi M. Chem. Rev. 2008; 108: 3054-3054
- 1g Beccalli EM, Broggini G, Martinelli M, Sottocornola S. Chem. Rev. 2007; 107: 5318-5318
- 1h Corbet J.-P, Mignani G. Chem. Rev. 2006; 106: 2651-2651
- 1i Beletskaya IP. Pure Appl. Chem. 2005; 77: 2021-2021
- 2a Iizuka K, Akahane K, Momose D, Nakazawa M, Tanouchi T, Kawamura M, Ohyama I, Kajiwara I, Iguchi Y. J. Med. Chem. 1981; 24: 1139-1139
- 2b Wolef JP, Wagaw S, Marcoux J, Buchwald S. Acc. Chem. Res. 1998; 31: 805-805
- 3a Wolef JP, Wagaw S, Marcoux J, Buchwald S. Acc. Chem. Res. 1998; 31: 805-805
- 3b Yang BH, Buchwald SL. J. Organomet. Chem. 1999; 576: 125-125
- 5 Prashad M, Hu B, Lu Y, Draper R, Har D, Repic O, Blacklock TJ. J. Org. Chem. 2000; 65: 2612-2612
- 6a Chan DM. T, Monaco KL, Wang RP, Winters MP. Tetrahedron Lett. 1998; 39: 2933-2933
- 6b Evan DA, Katz JL, West TR. Tetrahedron Lett. 1998; 39: 2937-2937
- 6c Lam PY. S, Clark CG, Saubern S, Adams J, Winters MP, Chan DM. T, Combs A. Tetrahedron Lett. 1998; 39: 2941-2941
- 6d Chan DM. T, Lam PY. S. In Boronic Acids . Wiley-VCH; Weinheim: 2005. Chap. 5
- 6e Qiao JX, Lam PY. S. Synthesis 2011; 829-829
- 6f Kantam ML, Reddy CV, Srinivas P, Bhargava S. Topics in Organometallic Chemistry 2013; 46: 119-119
- 6g Ley SV, Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400-5400
- 6h Rao KS, Wu T.-S. Tetrahedron 2012; 68: 7735-7735
- 7 Boronic Acids. Hall DG. Wiley-VCH; Weinheim: 2005
- 8 Lam PY. S, Vincent G, Clark CG, Deudon S, Jadhav PK. Tetrahedron Lett. 2001; 42: 3415-3415
- 9 Antilla JC, Buchwald SL. Org. Lett. 2001; 3: 2077-2077
- 10a Rossi SA, Shimkin KW, Xu Q, Mori-Quiroz LM, Watson DA. Org. Lett. 2013; 15: 2314-2314
- 10b Hugel HM, Rix CJ, Fleck K. Synlett 2006; 2290-2290
- 11 Mondal M, Sarmah G, Gogoi K, Bora U. Tetrahedron Lett. 2012; 53: 6219-6219
- 12 Moessner C, Bolm C. Org. Lett. 2005; 7: 2667-2667
- 13a Alonso F, Moglie Y, Radivoy G. Acc. Chem. Res. 2015; 48: 2516-2516
- 13b Gawande MB, Goswami A, Felpin FX, Asefa T, Huang X, Silva R, Zou X, Zboril R, Varma RS. Chem. Rev. 2016; 116: 3722-3722
- 14a Zhang Q, Zhang K, Xu D, Yang G, Huang H, Nie F, Liu C, Yang S. Prog. Mater. Sci. 2014; 60: 208-208
- 14b Singh J, Kaur G, Rawat M. J. Bioelectron. Nanotechnol. 2016; 1: 9-9
- 14c Kantam ML, Manorama SV, Basak P, Chintareddy VR, Bhargava S. In Manipulation of Nanoscale Materials: An Introduction to Nanoarchitectonics . In RSC Nanoscience & Nanotechnology Series No. 24 . Royal Society of Chemistry; Cambridge: 2012. Chap. 6
- 15a Lgnier P, Bellabarba R, Tooze RP. Chem. Soc. Rev. 2012; 41: 1708-1708
- 15b Tran TH, Nguyen VT. Int. Scholarly Res. Not. 2014;
- 15c Wang L, Cheng W, Gong H, Wang C, Wang D, Tang K, Qian Y. J. Mater. Chem. 2012; 22: 11297-11297
- 16 Goswami A, Raul PK, Purkait MK. Chem. Eng. Res. Des. 2012; 90: 1387-1387 . Modified Procedure for Preparing CuO NPs Copper(II) chloride dihydrate (6.8 g), NaOH (3.2 g), and capping solvent (polyethylene glycol) were mixed in a 2:1:1.5 ratio with EtOH–H2O (1:1, v/v, 200 mL) in a round-bottom flask fitted with a reflux condenser. The mixture was heated to reflux for 12 h and allowed to cool to r.t. Then the mixture was again heated to reflux for 5 h. The dark brown precipitate was centrifuged and washed with EtOH, acetone, and hot H2O sequentially. Finally, the product was dried at r.t, heated to 120 °C in a vacuum oven and allowed to cool to r.t.
- 17 Kliche G, Popovic ZV. Phys. Rev. B 1990; 42: 10060-10060
- 18a Lam PY. S, Vincent G, Clark CG, Deudon S, Jadhav PK. Tetrahedron Lett. 2001; 42: 3415-3415
- 18b Lam PY. S, Clark CG, Saubern S, Adams J, Averill KM, Chan DM. T, Combs A. Synlett 2000; 674-674
- 19 Typical Procedure: N-Arylation of Aniline with Phenylboronic Acid In a 50 mL round-bottomed flask, aniline (0.5 mmol), phenylboronic acid (1 mmol), K2CO3 (1.5 mmol), nanocatalyst (30 mol% with respect to aniline substrate) were added and stirred in MeOH–H2O (1:1) under air at r.t. for the required time, monitoring by TLC. After completion, the mixture was diluted with H2O, and the product was extracted with EtOAc (3×). The combined extracts were washed with brine (3×) and dried over Na2SO4. The product was purified by column chromatography (60–120 mesh silica gel, eluting with EtOAc–hexane solvent). The product was a grey crystalline solid, mp 54 °C; isolated yield: 92%. 1H NMR (400 MHz, CDCl3): δ = 5.63 (br s, 1 H), 6.90 (t, J = 8 Hz, 2 H), 7.04–7.02 (m, 4 H), 7.25–7.21 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.2, 129.5, 121.1, 117.9 ppm.
- 20 Typical Procedure: N-Arylation of Imidazole with Phenylboronic Acid In a 50 mL round-bottomed flask, imidazole (1 mmol), phenylboronic acid (1.2 mmol), K2CO3 (1.5 mmol), nanocatalyst (15 mol% with respect to imidazole substrate) were added and stirred in MeOH–H2O (1:1) under air at r.t. for the required time, monitoring by TLC. After completion, the mixture was diluted with H2O and the product was extracted with EtOAc (3×). The combined extracts were washed with brine (3×) and dried over Na2SO4. The product was purified using column chromatography (60–120 mesh silica gel, eluting with EtOAc–hexane). The product was isolated as white solid. 1H NMR (400 MHz, CDCl3): δ = 7.87 (s, 1 H), 7.50–7.47 (m, 2 H), 7.40–7.35 (m, 3 H), 2.28 (m, 1 H), 7.21 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.4, 135.6, 130.3, 129.9, 127.6, 121.6, 118.3 ppm.
- 21a Gogoi A, Sarmah G, Dewan A, Bora U. Tetrahedron Lett. 2014; 55: 31-31
- 21b Zhu X, Ma Y, Su L, Song H, Chen G, Liang D, Wan Y. Synthesis 2006; 3955-3955
- 21c Sun W.-B, Zhang P.-Z, Jiang T, Li C.-K, An L.-T, Shoberu A, Zou J.-P. Tetrahedron 2016; 72: 6477-6477
- 21d Sugimura H, Kondoh A. CN 101587308, 2009
- 21e Quach TD, Batey RA. Org. Lett. 2003; 5: 4397-4397
- 21f Qian G, Li X, Wang ZY. J. Mater. Chem. 2009; 19: 522-522
- 21g Lan J.-B, Chen L, Yu X.-Q, You J.-S, Xie R.-G. Chem. Commun. 2004; 188-188
- 21h Ueda S, Su M, Buchwald SL. J. Am. Chem. Soc. 2012; 134: 700-700
- 21i Garnier T, Sakly R, Danel M, Chassaing S, Pale P. Synthesis 2016; 49: 1223-1223
- 21j Li Z, Meng F, Zhang J, Xie J, Dai B. Org. Biomol. Chem. 2016; 14: 10861-10861
- 21k Ge X, Chen X, Qian C, Zhou S. RSC Adv. 2016; 6: 58898-58898
- 21l Zhu X, Su L, Huang L, Chen G, Wang J, Song H, Wan Y. Eur. J. Org. Chem. 2009; 635-635
- 22 Analytical Data for 4-Bromo-N-(4-fluorophenyl)benzenamine (Table 3, Entry 3) Colorless crystals; mp 43 °C. 1H NMR (400 MHz, CDCl3): δ = 5.54 (br s, 1 H), 7.32–7.25 (m, 2 H), 7.02–6.96 (m, 4 H), 6.82 (d, J = 8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.3, 132.2, 121.3, 121.2, 118.1, 116.2, 116.0, 112.2 ppm.
For reviews on Chan–Lam reaction: see: