Transition-Metal-Free Synthesis of Quinoxalines from o-Phenylenediamines and Arylacetaldehydes under Basic Conditions

Jinli Song; Xiaolong Li; Yongxin Chen; Mingming Zhao; Yani Dou; Baohua Chen

doi:10.1055/s-0031-1290450

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(16): 2416-2420
DOI: 10.1055/s-0031-1290450

letter

Transition-Metal-Free Synthesis of Quinoxalines from o-Phenylenediamines and Arylacetaldehydes under Basic Conditions

Jinli Song

^aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu, Lanzhou 730000, P. R. of China

^bKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582 eMail: chbh@lzu.edu.cn

,

Xiaolong Li

^aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu, Lanzhou 730000, P. R. of China

^bKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582 eMail: chbh@lzu.edu.cn

,

Yongxin Chen

^aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu, Lanzhou 730000, P. R. of China

^bKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582 eMail: chbh@lzu.edu.cn

,

Mingming Zhao

^aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu, Lanzhou 730000, P. R. of China

^bKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582 eMail: chbh@lzu.edu.cn

,

Yani Dou

^aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu, Lanzhou 730000, P. R. of China

^bKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582 eMail: chbh@lzu.edu.cn

,

Baohua Chen*

^aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu, Lanzhou 730000, P. R. of China

^bKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582 eMail: chbh@lzu.edu.cn

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

A novel method for the synthesis of quinoxalines via transition-metal-free cyclization of o-phenylenediamine and arylacetaldehyde in a one-pot procedure has been developed. In this process, an inorganic base (K₂CO₃) is the only reagent required, and it proceeds smoothly in the absence of adding transition metal catalysts. The reaction appears to be very general and suitable for the construction of a variety of quinoxalines.

Key words

quinoxalines - o-phenylenediamine - arylacetaldehyde - oxidation - condensation - transition-metal-free

Volltext

Referenzen

References and Notes

1a Nasr MN. A. Arch. Pharm. 2002; 335: 389
1b Yan L, Liu FW, Dai GF, Liu H. Bioorg. Med. Chem. Lett. 2007; 17: 609

2 Dell A, Williams DH, Morris HR, Smith GA, Feeney J, Roberts GC. K. J. Am. Chem. Soc. 1975; 97: 2497
3 Thomas KR. J, Lin JT, Tao YT, Chuen CH. J. Mater. Chem. 2002; 12: 3516
4 Hirayama T, Yamasaki S, Ameku H, Ishi-i T, Thiemann T, Mataka S. Dyes Pigm. 2005; 67: 105

5a He W, Meyers MR, Hanney B, Spada A, Blider G, Galzeinski H, Amin D, Needle S, Page K, Jayyosi Z, Perrone H. Bioorg. Med. Chem. Lett. 2003; 13: 3097
5b Kim YB, Kim YH, Park JY, Kim SK. Bioorg. Med. Chem. Lett. 2004; 14: 541

6a Porter AE. A In Comprehensive Heterocyclic Chemistry . Katritzky AR, Rees CW. Pergamon; Oxford: 1984: 157
6b Chen Z, Zhu J, Xie H, Li S, Wu Y, Gong Y. Adv. Synth. Catal. 2010; 352: 1296
6c Maryin LJ, Marzinzik AL, Ley SV, Baxendale LR. Org. Lett. 2011; 13: 320
6d Tang W, Xu L, Fan Q.-H, Wang J, Fan B, Zhou Z, Lam K.-h, Chan AS. C. Angew. Chem. Int. Ed. 2009; 48: 9135
6e Wan J, Gan S, Wu J, Pan Y. Green Chem. 2009; 11: 1633
6f Rueping M, Tato F, Schoepke FR. Chem.–Eur. J. 2011; 16: 2688
6g Raw SA, Wilfred CD, Taylor RJ. K. Org. Biomol. Chem. 2004; 2: 788
6h Sithambaram S, Ding Y, Li W, Shen X, Gaenzler F, Suib SL. Green Chem. 2008; 10: 1029

7 Bost RW, Towell EE. J. Am. Chem. Soc. 1948; 70: 903
8 Mousset C, Provot O, Hamze A, Bignon J, Brion J, Alami M. Tetrahedron 2008; 64: 4287
9 Wang LM, Liu JJ, Tian H, Qian CT. Synth. Commun. 2004; 34: 1349
10 Yadav J, Reddy B, Premalatha K, Shankar K. Synthesis 2008; 3787
11 More SV, Sastry MN. V, Yao CF. Green Chem. 2006; 8: 91
12 Cho C, Oh S. Tetrahedron Lett. 2006; 47: 5633
13 Cai J, Zou J, Pan X, Zhang W. Tetrahedron Lett. 2008; 49: 7386
14 Cho CS, Ren WS, Shin SC. Tetrahedron Lett. 2007; 48: 4665
15 Padmavathy K, Nagendrappa G, Geetha KV. Tetrahedron Lett. 2011; 52: 544
16 Wang W, Sheng YW, Meng X, Zhao M, Chen Y, Chen BH. Org. Lett. 2011; 13: 4514
17 Li H, Wang L, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2012; 51: 2943
18 Inamoto K, Asano N, Nakamura Y, Yonemoto M, Kondo Y. Org. Lett. 2012; 14: 2622
19 Zhang C, Xu Z, Zhang L, Jiao N. Angew. Chem. Int. Ed. 2011; 50: 11088

20a Zhou L, Shi Y, Xiao Q, Liu YZ, Ye F, Zhang Y, Wang JB. Org. Lett. 2011; 13: 968
20b Hamada T, Ye X, Stahl SS. J. Am. Chem. Soc. 2008; 130: 833
20c Xiao Q, Xia Y, Li H, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2011; 50: 1114

21 The crystal structure of 3ea (C₁₄H₉ClN₂) has been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number 887263.
22 General Procedure of the Reaction between o-Phenylenediamines and Arylacetaldehydes – Synthesis of 2-Phenylquinoxaline (3aa) o-Phenylenediamine (1a, 27 mg, 0.25 mmol), phenylacetaldehyde (2a, 58 μL, 0.5 mmol), K₂CO₃ (69 mg, 0.5 mmol), and toluene (2 mL) were added to a flask with a magnetic stirred bar. The reaction mixture was stirred for 8 h at 90 °C. The solution was then cooled to r.t., diluted with EtOAc and filtered. The filtrate was removed under the reduced pressure to get the crude product. The crude product was purified by column chromatography on silica gel (PE–EtOAc = 20:1) to afford 3aa (83% yield) as light yellow solid; mp 62–64 °C. ¹H NMR (300 MHz, CDCl₃): δ = 9.32 (s, 1 H), 8.20–7.80 (m, 4 H), 7.79–7.71 (m, 2 H), 7.59–7.51 (m, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 151.8, 143.3, 142.2, 141.5, 136.7, 130.2, 130.1, 129.6, 129.5, 129.1, 127.5 ppm. ESI-HRMS: m/z calcd for C₁₄H₁₀N₂ [M + H]⁺: 207.0917; found: 207.0913.

Zusatzmaterial

Supporting Information