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 2014; 25(14): 2030-2032
DOI: 10.1055/s-0034-1378377
DOI: 10.1055/s-0034-1378377
letter
Synthesis of Pyrroles and Thiazolanes Promoted by N-Methylimidazole in Water
Further Information
Publication History
Received: 22 April 2014
Accepted after revision: 30 May 2014
Publication Date:
16 July 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201414/lookinside/thumbnails/10.1055-s-0034-1378377-1.jpg)
Abstract
A convenient and efficient approach to the synthesis of substituted pyrroles is reported based on three-component reaction of primary amines and alkyl propiolates in the presence of N-methylimidazole in water. A water-accelerated synthesis of thiazolane derivatives has also been established by employing the three-component reaction of primary amines, alkyl propiolates, and isothiocyanates in the presence of N-methylimidazole.
-
References and Notes
- 1 Anastas P, Williamson T. Green Chemistry, Frontiers in Benign Chemical Synthesis and Procedures . Oxford Science Publications; New York: 1998
- 2 Cave GW. V, Raston CL, Scott JL. Chem. Commun. 2001; 2159
- 3 Sheldon RA. Chem. Ind. 1997; 12
- 4 Multicomponent Reactions . Zhu J, Bienayme H. Wiley-VCH; Weinheim: 2005
- 5 Torok M, Abid M, Mhadgut SC, Torok B. Biochemistry 2006; 45: 5377
- 6 Sundberg RJ In Comprehensive Heterocyclic Chemistry . Katritzky A, Rees CW, Scriven EF. V. Pergamon; Oxford: 1996
- 7 Tao H, Hwang I, Boger DL. Bioorg. Med. Chem. Lett. 2004; 14: 5979
- 8 Baumgarten M, Tyutyulkov N. Chem. Eur. J. 1998; 4: 987
- 9 Lehuede J, Fauconneau B, Barrier L, Ourakow M, Piriou A, Vierfond JM. Eur. J. Med. Chem. 1999; 34: 991
- 10 Burli RW, Jones P, McMinn D, Le Q, Duan JX, Kaizerman JA, Difuntorum S, Moser HE. Bioorg. Med. Chem. Lett. 2004; 14: 1259
- 11 Jonas R, Klockow M, Lues I, Pruecher H, Schliep HJ, Wurziger H. Eur. J. Med. Chem. 1993; 28: 129
- 12 Denny WA, Rewcastle GW, Baguley BC. J. Med. Chem. 1990; 33: 814
- 13 Demopoulos VJ, Rekka E. J. Pharm. Sci. 1995; 84: 79
- 14 Del Poeta M, Schell WA, Dykstra CC, Jones S, Tidwell RR, Czarny A, Bajic M, Kumar A, Boykin D, Perfect JR. Antimicrob. Agents Chemother. 1998; 42: 2495
- 15 Khlebnikov AF, Golovkina MV, Novikov MS, Yufit DS. Org. Lett. 2012; 14: 3768
- 16 Das B, Reddy GC, Balasubramanyan P, Veeranjaneyulu B. Synthesis 2010; 1625
- 17 Liu W, Jiang H, Huang L. Org. Lett. 2010; 12: 312
- 18 Morin MS. T, Arndtsen BA. Org. Lett. 2010; 12: 4916
- 19 Herath A, Cosford ND. P. Org. Lett. 2010; 12: 5182
- 20 Ciez D. Org. Lett. 2009; 11: 4282
- 21 General Procedure for the Preparation of Compounds 4 To a stirred mixture of alkyl propiolate 1 (2 mmol) and primary amine 2 (2 mmol) in H2O (5 mL) was added a mixture of alkyl propiolate 1 and N-methylimidazole (3, 5 mol%) in H2O (5 mL). The reaction mixture was then stirred for 1.5 h at 50 °C. After completion of the reaction (1.5 h; TLC; EtOAc–hexane = 1:4), the solid residue was filtered and washed with cold Et2O to give pure product 4. Dimethyl 1-Methyl-1H-pyrrole-3,4-dicarboxylate (4a) Pale yellow powder, yield 0.36 g (92%). IR (KBr): 1735, 1729, 1587, 1435, 1295, 1126 cm–1. 1H NMR (500 MHz, CDCl3): δ = 3.58 (3 H, s, NMe), 3.78 (6 H, s, 2 MeO), 6.92 (2 H, s, 2 CH) ppm. 13C NMR(125.7 MHz, CDCl3): δ = 35.8 (NMe), 51.8 (2 MeO), 137.2 (2 C), 138.3 (2 CH), 165.4 (2 C=O) ppm. MS (EI): m/z (%) = 197 (15) [M+], 135 (85), 79 (64), 31 (100). Anal. Calcd for C9H11NO4 (197.19): C, 54.82; H, 5.62; N, 7.10. Found: C, 54.93; H, 5.74; N, 7.22.
-
22 Breslow R. J. Am. Chem. Soc. 1958; 80: 3719
- 23 Miwatashi S, Arikawa Y, Kotani E, Miyamoto M, Naruo KI, Kimura H, Tanaka T, Asahi S, Ohkawa S. J. Med. Chem. 2005; 48: 5966
- 24 Papadopoulou C, Geronikaki A, Hadjipavlou-Litina D. Il Farmaco 2005; 60: 969
- 25 Kumar Y, Green R, Borysko KZ, Wise DS, Wotring LL, Townsend LB. J. Med. Chem. 1993; 36: 3843
- 26 Pereira R, Gaudon C, Iglesias B, Germain P, Gronemeyer H, de Lera AR. Bioorg. Med. Chem. Lett. 2006; 16: 49
- 27 Tsurumi Y, Ueda H, Hayashi K, Takase S, Nishikawa M, Kiyoto S, Okuhara M. J. Antibiot. 1995; 48: 1066
- 28 Bell FW, Cantrell AS, Hoberg M, Jaskunas SR, Johansson NG, Jordon CL, Kinnick MD, Lind P, Morin JM. J. Med. Chem. 1995; 38: 4929
- 29 Millan DS, Prager RH, Brand C, Hart PH. Tetrahedron 2000; 56: 811
- 30 Wang WL, Yao DY, Gu M, Fan MZ, Li JY, Xing YC, Nan FJ. Bioorg. Med. Chem. Lett. 2005; 15: 5284
- 31 Hossaini Z, Rostami-Charati F, Eslami Moghadam M, Moghaddasi-Kochaksaraee F. Chin. Chem. Lett. 2014; 25: 794
- 32 General Procedure for the Preparation of Compounds 13 To a magnetically stirred mixture of acetylene 1 (2 mmol) and N-methylimidazole (3, 5 mol%) in H2O (5 mL) was added a mixture of isothiocyanate 12 and primary amine 2 (2 mmol) in H2O (5mL) at r.t. The reaction mixture was then stirred. After the completion of the reaction (6 h; TLC; EtOAc–hexane = 1:7), the solid residue was filtered and washed with cold Et2O to afforded pure compounds 13. Methyl 2-(Methylimino)-1,3-thiazolane-5-dicarboxylate (13a) Yellow powder, mp 164–166 °C, yield 0.26 g (75%). IR (KBr) νmax = 1738, 1567, 1456, 1385, 1257 cm–1. 1H NMR (500 MHz, CDCl3): δ = 3.24 (3 H, s, NMe), 3.75 (3 H, s, MeO), 3.87 (1 H, dd, 2 J HH = 16 Hz, 3 J HH = 7 Hz, CH), 4.12 (1 H, dd, 2 J HH =16 Hz, 3 J HH = 3 Hz, CH), 4.78 (1 H, dd, 3 J HH = 7 Hz 3 J HH = 3 Hz, CH), 6.14 (1 H, br, NH) ppm. 13C NMR (125.7 MHz, CDCl3): δ = 35.8 (NMe), 39.4 (CH), 47.5 (CH2), 52.4 (MeO), 163.2 (C=N), 172.5 (C=O) ppm. MS: m/z (%) = 174 (15) [M+], 143 (84), 31 (100). Anal. Calcd (%) for C6H10N2O2S (174.22): C, 41.36; H, 5.79; N, 16.08. Found: C, 41.24; H, 5.62; N, 15.96.
- 33 Yavari I, Souri S, Sirouspour M. Synlett 2008; 1633