Synthesis of Biaryl Derivatives via a Magnetic Pd-NPs-Catalyzed One-Pot 
Diazotization–Cross-Coupling Reaction

Yan Zong; Jiefeng Hu; Peipei Sun; Xiaoqing Jiang

doi:10.1055/s-0032-1317097

Synlett, Table of Contents

Synlett 2012; 23(16): 2393-2396
DOI: 10.1055/s-0032-1317097

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Synthesis of Biaryl Derivatives via a Magnetic Pd-NPs-Catalyzed One-Pot Diazotization–Cross-Coupling Reaction

Yan Zong

^aJiangsu Key Laboratory of Biofunctional Materials, College of Chemistry and Materials Science, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210097, P. R. of China, Email: jiangxiaoqing@njnu.edu.cn

,

Jiefeng Hu

^aJiangsu Key Laboratory of Biofunctional Materials, College of Chemistry and Materials Science, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210097, P. R. of China, Email: jiangxiaoqing@njnu.edu.cn

,

Peipei Sun*

^aJiangsu Key Laboratory of Biofunctional Materials, College of Chemistry and Materials Science, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210097, P. R. of China, Email: jiangxiaoqing@njnu.edu.cn

^bKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. of China, Fax: +86(25)85891767 Email: sunpeipei@njnu.edu.cn

,

Xiaoqing Jiang*

^aJiangsu Key Laboratory of Biofunctional Materials, College of Chemistry and Materials Science, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210097, P. R. of China, Email: jiangxiaoqing@njnu.edu.cn

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Abstract

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Abstract

A magnetic Pd-NPs-catalyzed one-pot diazotization–cross-coupling reaction of anilines and arylboronic acids was developed. Biaryl derivatives were therefore synthesized in good to excellent yields. Through magnetic separation, the catalyst could be recovered and reused for five times. There were several obvious advantages such as broad applicability, high selectivity, simply experimental operation as well as the convenient preparation, high efficiency and reusability of catalyst.

Key words

nanopalladium - catalysis - diazotization - cross-coupling - magnetic separation

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References

References and Notes

For partial reviews on Suzuki–Miyaura reaction, see:

1a Suzuki A. Acc. Chem. Res. 1982; 15: 178
1b Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
1c Corbet JP, Mignani G. Chem. Rev. 2006; 106: 2651
1d McGlacken GP, Bateman LM. Chem. Soc. Rev. 2009; 38: 2447
1e Xue L, Lin Z. Chem. Soc. Rev. 2010; 39: 1692

2a Zollinger H. Diazo Chemistry I: Aromatic and Heteroaromatic Compounds. John Wiley and Sons; New York: 1994
2b Roglans A, Pla-Quintana A, Moreno-Mañas M. Chem. Rev. 2006; 106: 4622

3a Wu XF, Neumann H, Beller M. Chem. Commun. 2011; 47: 7959
3b Callonnec FL, Fouquet E, Felpin FX. Org. Lett. 2011; 13: 2646
3c Mo FY, Qiu D, Jiang YB, Zhang Y, Wang JB. Tetrahedron Lett. 2011; 52: 518

For partial reviews on transition-metal nanoparticles catalysis, see:

4a Moreno-Mañas M, Pleixats R. Acc. Chem. Res. 2003; 36: 638
4b Astruc D, Lu F, Aranzaes JR. Angew. Chem. Int. Ed. 2005; 44: 7852
4c Astruc D. Inorg. Chem. 2007; 46: 1884
4d Ferrando R, Jellinek J, Johnston RL. Chem. Rev. 2008; 108: 845
4e Pachon LD, Rothenberg G. Appl. Organometal. Chem. 2008; 22: 288
4f Balanta A, Godard C, Claver C. Chem. Soc. Rev. 2011; 40: 4973
4g Fihri A, Bouhrara M, Nekoueishahraki B, Basset JM, Polshettiwar V. Chem. Soc. Rev. 2011; 40: 5181

5a Li YG, Zhou P, Dai ZH, Hu ZX, Sun PP, Bao JC. New J. Chem. 2006; 30: 832
5b Zhou P, Li YG, Sun PP, Zhou JH, Bao JC. Chem. Commun. 2007; 1418
5c Feng LZ, Liu FX, Sun PP, Bao JC. Synlett 2008; 1415
5d Feng LZ, Gan ZY, Nie XP, Sun PP, Bao JC. Catal. Commun. 2010; 11: 555
5e Nie XP, Liu SL, Zong Y, Sun PP, Bao JC. J. Organomet. Chem. 2011; 696: 1570

6a Lim CW, Lee IS. Nano Today 2010; 5: 412
6b Hu AG, Yee GT, Lin WB. J. Am. Chem. Soc. 2005; 127: 12486
6c Jin MJ, Lee DH. Angew. Chem. Int. Ed. 2010; 49: 1119
6d Amali AJ, Rana RK. Green Chem. 2009; 11: 1781
6e Jang Y, Chung J, Kim S, Jun SW, Kim BH, Lee DW, Kim BM, Hyeon T. Phys. Chem. Chem. Phys. 2011; 13: 2512

7 Hu JF, Wang YP, Han M, Zhou YM, Sun PP, Jiang XQ. Catal. Sci. Tech. 2012; in press; DOI: 10.1039/ C2CY20263H

8a Flood DT. Org. Synth. 1943; 2: 295
8b Schiemann G, Winkelmüller W. Org. Synth. 1943; 2: 299
8c Doyle MP, Bryker WJ. J. Org. Chem. 1979; 44: 1572

9 Typical Procedure for the One-Pot Diazotization–Cross-Coupling Reaction To a Schlenk tube (15 mL) initially fitted with arylamine (0.5 mmol) and MeOH (3 mL) at 0 °C were added t-BuONO (0.075 mL, 0.6 mmol) and BF₃·OEt₂ (0.013 mL, 0.1 mmol). The resulting mixture was stirred for 30 min at 0 °C. To the reaction mixture, kept at 0 °C, were sequentially added arylboronic acid (1 mmol), Pd/Fe₃O₄/s-graphene (3.2 mg, 0.5 mol%). The reaction mixture was allowed to reach 60 °C and stirred for 5 h. After completion of the reaction, the catalyst was recovered by magnetic separation. The solution was diluted with H₂O (10 mL) and extracted with EtOAc (3 × 10 mL). The organic layers were combined, dried over anhyd Na₂SO₄, and purified by column chromatography on silica gel with hexane–EtOAc (10:1) as eluent to yield the pure product. The precipitate was further washed sufficiently with MeOH and Et₂O, and the Pd nanoparticles were recovered for the further use. Ethyl biphenyl-4-carboxylate ¹H NMR (400 MHz, CDCl₃): δ = 1.45 (t, J = 7.1 Hz, 3 H), 4.42 (q, J = 7.1 Hz, 2 H), 7.41–7.44 (m, 1 H), 7.48–7.52 (m, 2 H), 7.65–7.70 (m, 4 H), 8.16 (d, J = 7.9 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 14.3, 60.9, 127.0, 127.2, 128.1, 128.9, 129.2, 130.0, 140.0, 145.5, 166.5. 4-Bromo-4′-methoxybiphenyl ¹H NMR (400 MHz, CDCl₃): δ = 3.86 (s, 3 H), 7.00 (d, J = 7.7 Hz, 2 H), 7.43 (d, J = 7.8 Hz, 2 H), 7.50–7.56 (m, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 55.3, 114.3, 120.7, 127.9, 128.3, 131.7, 132.5, 139.7, 159.4

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