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 2016; 27(15): 2217-2220
DOI: 10.1055/s-0035-1561663
DOI: 10.1055/s-0035-1561663
letter
SnCl2·2H2O-Catalyzed Solvent-Free Synthesis of α-Amino Ketones and Tetrasubstituted Pyrazines
Further Information
Publication History
Received: 20 April 2016
Accepted after revision: 11 May 2016
Publication Date:
22 June 2016 (online)
Abstract
Solvent-free reaction of various anilines with α-hydroxy ketones catalyzed by SnCl2·2H2O provides α-amino ketones in excellent yields. While a similar reaction with aliphatic amines is applicable for the synthesis of substituted pyrazines, SnCl2·2H2O permits versatility in the solvent-free reaction of α-hydroxy ketones with ammonium acetate to give the corresponding substituted pyrazines in good to excellent yields.
Key words
pseudo-four-component reaction - α-amino ketone - α-hydroxy ketone - SnCl2·2H2O - aromatic amines - pyrazineSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561663.
- Supporting Information
-
References and Notes
- 1 Sardina FJ, Rapoport H. Chem. Rev. 1996; 96: 1825
- 2a Bodtke A, Langer P. Tetrahedron Lett. 2004; 45: 8741
- 2b Medaer BP, Hoornaert GJ. Tetrahedron 1999; 55: 3987
- 2c Chandrashaker V, Taniguchi M, Ptaszek M, Lindsey JS. Tetrahedron 2012; 68: 6957
- 2d Bryan L, Richard A, Buzon KF, Chiu T, Colgan ML, Kasthurikrishnan N. Tetrahedron Lett. 2004; 45: 6887
- 2e Japp FR, Murray TS. J. Chem. Soc., Trans. 1894; 65: 889
- 3 Perrine DM, Ross JT, Nervi SJ, Zimmerman RH. J. Chem. Edu. 2000; 77: 1479
- 4a Lee I, Whang LH, Yu KY. Bull. Korean Chem. Soc. 2003; 24: 993
- 4b Kirrmann A, Nouri Bimorghi R, Elkik E. Bull. Soc. Chim. 1969; 55: 2385
- 4c Avenoza A, Busto JH, Peregrina M. Tetrahedron 2002; 58: 10167
- 4d Phukan P, Sudalai A. Tetrahedron: Asymmetry 1998; 9: 1001
- 4e Pfaltz A, Anwar S. Tetrahedron Lett. 1984; 25: 2977
- 4f Reddy MS, Narender M, Rama RK. Tetrahedron Lett. 2005; 46: 1299
-
4g Murry JA, Frantz DE, Soheili A, Tillyer R, Grabowski EJ, Reider PJ. J. Am. Chem. Soc. 2001; 123: 9696
- 4h Miura T, Biyajima T, Fujii T, Murakami M. J. Am. Chem. Soc. 2012; 134: 194
- 4i Chen H, Fan G, Li S, Mao K, Liu Y. Tetrahedron Lett. 2014; 55: 1593
- 4j Castells J, Lopez Calahorra F, Bassedas M, Urrios P. Synthesis 1988; 14: 314
- 4k Liu J, Ikemoto N, Petrillo D, Armstrong DJ. Tetrahedron Lett. 2002; 43: 8223
- 4l Goha S, Rajeshkumar V, Kotha SS. Sekar G. Org. Lett. 2015; 17: 406
- 4m Shipton MR. Synlett 1992; 491
- 4n Lachowicz B. Monatsh. Chem. 1893; 14: 279
- 5 Conrad K, Hsiao Y, Miller R. Tetrahedron Lett. 2005; 46: 8587
- 6 Nasaehzadeh A, Chahardoli A. Chin. J. Chem. 2000; 18: 608
- 7 Smith HE, Hicks AA. J. Org. Chem. 1971; 36: 3659
- 8a Meher CP, Rao AM, Omar Md. Asian J. Pharm. Sci. Res. 2013; 3: 43
- 8b Zhang Y.-B, Wang X.-L, Liu W, Yang Y.-S, Tang J.-F, Zhu H.-L. Bioorg. Med. Chem. 2012; 20: 6356
- 8c Maga JA, Sizer CE. J. Agric. Food Chem. 1973; 21: 22
- 9a Anand R, Rao BS. Catal. Commun. 2002; 3: 29
- 9b Miralinaghi P, Salimi M, Shirmohammadli S, Amini M. Int. J. Pharma Biosci. Technol. 2011; 3: 60
- 9c Jing F, Zhang Y, Luo S, Chu W, Zhang H, Shi X. J. Chem. Sci. 2010; 122: 621
- 9d Latha BM, Sadasivam V, Sivasankar B. Catal. Commun. 2007; 8: 1070
- 9e Fan L, Chen W, Qian C. Tetrahedron Lett. 2013; 54: 231
- 9f Kotharkar SA, Shinde DB. Chin. J. Chem. 2007; 25: 105
- 9g Ravindran G, Renganathan NG. Org. Commun. 2010; 3: 76
- 9h Chen Z, Ye D, Xu G, Ye M, Liu L. Org. Biomol. Chem. 2013; 11: 6699
- 9i Viswanadham KD. R, Reddy MP, Sathyanarayana P, Ravi O, Kant R, Bathula SR. Chem. Commun. 2014; 50: 13517
- 9j Petrosyan A, Ehlers P, Surkus AE, Ghochikyan TV, Saghyan AS, Lochbrunner S, Langer P. Org. Biomol. Chem. 2016; 14: 1442
- 9k Petrosyan A, Ehlers P, Reimann S, Ghochikyan TV, Saghyan AS, Spannenberg A, Lochbrunner S, Langer P. Tetrahedron 2015; 71: 6803
- 9l Alizadeh A, Hossein Abadi M, Ghanbaripour R. Synlett 2014; 25: 1705
- 9m Johannes E, Horbert R, Schlosser J, Schmidt D, Peifer C. Tetrahedron Lett. 2013; 54: 4067
- 9n Badrinarayanan S, Sperry J. Synlett 2011; 2339
- 9o Mohamed MN, Beheget SA. J. Kufa Chem. Sci. 2010; 1: 89
- 10a Ali H, Van Lier JE. Tetrahedron Lett. 2012; 53: 4824
- 10b Aravind K, Ganesh A, Ashok D. J. Chem. Pharm. Res. 2013; 5: 48
- 11 Marques MV, Ruthner MM, Fontoura LA, Russowsky D. J. Braz. Chem. Soc. 2012; 23: 171
- 12 Ferreira SB, Kaiser CR. Expert Opin. Ther. Pat. 2012; 22: 1033
- 13a Jiang B, Rajale T, Wever W, Tu SJ, Li G. Chem. Asian J. 2010; 11: 2318
- 13b Gu Y. Green Chem. 2012; 14: 2091
- 13c Kidwai M, Chauhan R. J. Mol. Catal. A: Chem. 2013; 377: 1
- 13d Dömling A, Wang W, Wang K. Chem. Rev. 2012; 112: 3083
- 13e Graaff C, Ruijte E, Orru RV. A. Chem. Soc. Rev. 2012; 41: 3969
- 13f Brauch S, Van Berkela SS, Westermann B. Chem. Soc. Rev. 2013; 42: 4948
- 13g Pirrung MC, Das Sarma K. J. Am. Chem. Soc. 2004; 126: 444
- 13h Gan S.-F, Wan J.-P, Pan Y.-J, Sun C.-R. Synlett 2010; 973
- 13i Gawande MB, Bonifácio VD. B, Luque R, Brancoa PS, Varma RS. Chem. Soc. Rev. 2013; 42: 5522
- 14 Aparicio D, Attanasi OA, Filippone P, Ignacio R, Lillini S, Mantellini F, Palacios F, de los Santos JM. J. Org. Chem. 2006; 71: 5897
- 15a Wang J, Yuan G, Dong CQ. Chem. Lett. 2004; 33: 286
- 15b Nagarapu L, Bantu R, Puttireddy R. Appl. Catal., A 2007; 332: 304
- 15c Upadhyay K, Mishra RK, Kumar A. Catal. Lett. 2008; 121: 118
- 15d Duan L.-P, Li Q, Wu N.-B, Xu D.-F, Zhang H.-B. Chin. Chem. Lett. 2014; 25: 155
- 15e Duan LP, Li Q, Wu NB, Xu DF, Zhang HB. Chin. Chem. Lett. 2014; 25: 155
- 15f Bellamy F, Ou K. Tetrahedron Lett. 1984; 25: 839
- 15g Nayal OS, Bhatt V, Sharma S, Kumar N. J. Org. Chem. 2015; 80: 5912
- 16a Tamaddon F, Nasiri A, Farokhi S. Catal. Commun. 2011; 12: 1477
- 16b Jafari AA, Amini S, Tamaddon F. J. Iran. Chem. Soc. 2013; 10: 677
- 16c Tamaddon F, Pouramini F. Synlett 2014; 25: 1127
- 16d Tamaddon F, Kargar-Shooroki H, Jafari AA. J. Mol. Catal A: Chem. 2013; 368
- 16e Tamaddon F, Farahi M. Synlett 2012; 23: 1379
- 16f Tamaddon F, Alizadeh M. Synlett 2015; 26: 525
- 16g Tamaddon F, Amirpoor F. Synlett 2013; 24: 1791
- 17 General Procedure for Synthesis of α-Amino Ketones SnCl2·2H2O (10 mol%) was added to a stirred mixture of benzoin (2 mmol) and amine (2 mmol) in a round-bottom flask at 80 °C. The resulting mixture was stirred for the given time and progress of the reaction was followed by TLC (EtOAc–hexane, 20:80). After completion of the reaction, EtOAc was added (50 mL), and the mixture was filtered to remove the catalyst. Then the organic layer was washed with 10% NaHCO3 and water, dried over Na2SO4, filtered, and concentrated to give the product. Although additional purification was not required in most cases, the crude products may be recrystallized from H2O–EtOH (60:40). Analytical Data for 2-[(4-Acetylphenyl)amino]-1,2-diphenylethanone (2j) Pale yellow solid; yield for reaction in 2 mmol scale: 300 mg (92%); mp 158–160 °C. FT-IR (KBr): 3375 (NH stretch), 1676, 1664 (C=O stretch), 1600, 1520, 1479, 1447, 1273, 1170 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 2.40 (s, 3 H), 5.49 (s, 1 H), 6.59 (d, J = 7.6 Hz, 1 H), 6.87 (d, J = 8.8 Hz, 2 H), 7.21–7.66 (m, 8 H), 7.71 (d, J = 8.8 Hz, 2 H), 8.17 (d, J = 7.2 Hz, 2 H) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 26.42, 61.07, 112.67, 126.89, 128.41, 128.52, 128.86, 129.24, 129.32, 129.34, 130.00, 130.09, 134.22, 135.15, 137.90, 137.92, 151.59, 195.75, 197.11 ppm. Anal. Calcd for C22H19NO2: C, 80.22; H, 5.81; N, 4.25; O, 9.71. Found: C, 80.25; H, 5.98; N, 4.27; O, 9.80.
-
18
General Procedure for Synthesis of Substituted Pyrazines
To a mixture of benzoin (2 mmol) and NH4OAc (2.2 mmol) was added SnCl2·2H2O (10 mol%), and the mixture was stirred for the requisite time at 80 °C. After completion of the reaction (TLC), EtOH (3 mL), and water (7 mL) were added, the mixture was stirred, and the product was isolated by filtration. The pyrazine products were analytically pure and showed the expected characterization data without additional purification.
Analytical Data
2,3,5,6-Tetraphenylpyrazine (1a) Yellow solid; yield for reaction at 2 mmol scale: 346 mg (90%); mp 252–254 °C. FT-IR (KBr): 3054, 1628 (C=N stretch), 1599, 1521, 1461, 1393, 1175, 1025 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.26–7.34 (m, HAr, 12 H), 7.65 (t, J = 6.8 Hz, HAr, 8 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 148.47, 138.52, 129.94, 128.62, 128.52, 128.30 ppm. 1,4-Dibenzyl-2,3,5,6-tetraphenyl-1,4-dihydropyrazine (20) Yellow solid; yield for reaction at 2 mmol scale: 510 mg (90%); mp 157–160 °C. FT-IR (KBr): 1601, 1448 (C=C stretch), 1027 (C–N stretch) cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 5.18 (s, 4 H), 6.77 (d, J = 6.8 Hz, 3 H), 7.15–7.25 (m, HAr, 9 H), 7.30–7.41 (m, HAr, 3 H), 7.43–7.49 (m, HAr, 12 H), 7.67–7.69 (m, HAr, 3 H) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 48.16, 106.28, 126.10, 126.58, 126.76, 127.68, 128.59, 129.02, 129.08, 129.32, 129.37, 129.43, 130, 68, 131.06, 131.25, 131.31, 135.00, 137.36, 137.79 ppm. Anal. Calcd for C42H34N2: C, 89.01; H, 6.05; N, 4.94. Found: C, 88.98; H, 6.03; N, 4.97. - 19 Nápoles-Escutary FA, Vale Capdevilla RM, Casals Hung M, Jaciel LO, Joyce J. Rev. Cubana Quim. 2012; 24: 261
- 20 Farahi M, Tammadon F, Karami B, Pasdar S. Tetrahedron Lett. 2015; 56: 1887
- 21 Mousavi M, Seyfi H. Org. Chem. J. 2011; 1: 17