Facile Conversion of Amino Acids into 1-Alkyl Imidazole-2-thiones, and Their Oxidative Desulfurization to Imidazoles with Benzoyl Peroxide

Derek M. Wolfe; Peter R. Schreiner

doi:10.1055/s-2007-983740

PAPER

Facile Conversion of Amino Acids into 1-Alkyl Imidazole-2-thiones, and Their Oxidative Desulfurization to Imidazoles with Benzoyl Peroxide

Derek M. Wolfe^a,b, Peter R. Schreiner*^a,b
^a Institut für Organische Chemie, Justus-Liebig-Universität, Heinrich-Buff-Ring 58, 35392 Gießen, Germany
Fax: +49(641)9934309; e-Mail: prs@org.chemie.uni-giessen.de;
^b Department of Chemistry, University of Georgia, 1001 Cedar St., Athens, GA 30602, USA
Fax: +1(706)5429454; e-Mail: prs@chem.uga.edu;

Abstract

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Abstract

Glycine was acylated with isothiocyanates and condensed to 3-alkyl 2-thiohydantoins, which were reduced with a mixture of sodium borohydride and lithium chloride and dehydrated to 1-alkyl imidazole-2-thiones. These were oxidatively desulfurized to imidazoles with benzoyl peroxide. No chromatography was required for model compounds. The methods developed were used to elaborate tyrosine to 1,4-di(p-methoxybenzyl)imidazole, a common intermediate in the syntheses of three imidazoles from the sponge Leucetta.

Key words

desulfurization - heterocycles - imidazoles - natural products - oxidation

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Referenzen

References

1 Hofmann K. Imidazole and its Derivatives Interscience Publishers; New York: 1953.

2 Review: Trzhtsinskaya BV. Abramova ND. Sulfur Rep. 1991, 10: 389

3 Xi N. Xu S. Cheng Y. Tasker AS. Hungate RW. Reider PJ. Tetrahedron Lett. 2005, 46: 7315

4 Baran PS. Shenvi RA. Mitsos CA. Angew. Chem. Int. Ed. 2005, 44: 3714

5 Loksha YM. El-barbary AA. El-badawi MA. Nielsen C. Pedersen EB. Synthesis 2004, 116

6 Chang JH. Lee KW. Nam DH. Kim WS. Shin H. Org. Process Res. Dev. 2002, 6: 674

7 Grivas S. Ronne E. Acta Chem. Scand. 1995, 49: 225

8 Karkhanis DW. Field L. Phosphorus, Sulfur Relat. Elem. 1985, 22: 49

9 Pesch J. Harms K. Bach T. Eur. J. Org. Chem. 2004, 2025

10 Frachey G. Crestini C. Bernini R. Saladino R. Mincione E. Heterocycles 1994, 38: 2621

11 Ashutosh Pandey ND. Mehrotra JK. Heterocycles 1979, 12: 1339

12 Buran V. Massaroli GG. Boll. Chim. Farm. 1980, 119: 725 ; Chem. Abstr. 1981, 95, 62075y

13 Hayakawa I. Yamazaki K. Dohmori R. Koga N. Heterocycles 1978, 10: 241

14 Jones RG. J. Am. Chem. Soc. 1952, 74: 1085

15 Tanaka K. Shimazak M. Murakami Y. Chem. Pharm. Bull. 1982, 30: 2714

16 Schoenherr HJ. Wanzlick HW. Chem. Ber. 1970, 103: 1037

17 Jones RG. Kornfeld EC. McLaughlin KC. Anderson RC. J. Am. Chem. Soc. 1949, 71: 4000

18 Kister J. Assef G. Mille G. Metzger J. Can. J. Chem. 1979, 57: 813

19 Marckwald W. Ber. Dtsch. Chem. Ges. 1892, 25: 2354

20 Kuhn N. Kratz T. Synthesis 1993, 561

21 Markwalder JA. Pottorf RS. Seitz SP. Synlett 1997, 521

22 Scott JE. Henderson G. Biochem. J. 1968, 109: 209

23 Johnson JR. Buchanan JB. J. Am. Chem. Soc. 1951, 73: 3749

24 Chang W.-J. Kulkarni MV. Sun C.-M. J. Comb. Chem. 2006, 8: 141

25 Zhang X. Allan GF. Sbriscia T. Linton O. Lundeen SG. Sui Z. Bioorg. Med. Chem. Lett. 2006, 16: 5763

26 Khodair AI. Nucleosides, Nucleotides Nucleic Acids 2001, 20: 1735

27 Reyes S. Burgess K. J. Org. Chem. 2006, 71: 2507

28 Muccioli GG. Fazio N. Scriba GKE. Poppitz W. Cannata F. Poupaert JH. Wouters J. Lambert DM. J. Med. Chem. 2006, 49: 417

29 Marckwald W. Neumark M. Stelzner R. Ber. Dtsch. Chem. Ges. 1891, 24: 3278

30 Edman P. Carlsberg Res. Commun. 1977, 42: 1 ; Chem. Abstr. 1977, 87, 163564x

31 Sun Y. Gao L.-P. Ding M.-W. Synth. Commun. 2006, 36: 1185

32 Sun Y. Gao L.-P. Guo Z.-Q. Ding M.-W. Phosphorus, Sulfur Silicon Relat. Elem. 2006, 181: 2109

33 Sundaram GSM. Venkatesh C. Ila H. Junjappa H. Synlett 2007, 251

34 Wolfe DM. Schreiner PR. Eur. J. Org. Chem. 2007, 2825

35 Kruse LI. Kaiser C. DeWolf WE. Finkelstein JA. Frazee JS. Hilbert EL. Ross ST. Flaim KE. Sawyer JL. J. Med. Chem. 1990, 33: 781

36 Gonzalez M. A. Mota J. F. Monterrey IM. G. Requejo JL. J. Albarran JC. P. Mellet MC. O. Carbohydr. Res. 1986, 154: 49

37 Yang C. Pittman CU. Synth. Commun. 1998, 28: 2027

38 Brown HC. Ichikawa K. J. Am. Chem. Soc. 1961, 83: 4372

39 Babler JH. Synth. Commun. 1982, 12: 839

40 Nakamura S. Kawasaki I. Yamashita M. Ohta S. Heterocycles 2003, 60: 583

41 Lipshutz BH. Huff B. Hagen W. Tetrahedron Lett. 1988, 29: 3411

42 Lipshutz BH. Vaccaro W. Huff B. Tetrahedron Lett. 1986, 27: 4095

43a Goodyer CLM. Chinje EC. Jaffar M. Stratford IJ. Threadgill MD. Bioorg. Med. Chem. 2003, 11: 4189

43b

The procedure was scaled up for the reaction of 4-methoxybenzylamine (25.92 g, 189 mmol), CaCO₃ (19.44 g, 194 mmol), and CSCl₂ (29 mL, 44 g, 383 mmol) in CHCl₃ (175 mL), and H₂O (175 mL). The isolate was distilled (bp 92.5-94 °C/0.2-0.3 Torr) to afford p-methoxybenzyl isothiocyanate (30.24 g, 89%) with spectral properties matching those of the chromatographed material from the literature.

44 Incesu Z. Benkli K. Akalin G. Kaplancikli ZA. Cell Biol. Int. 2004, 28: 267

45 Brown HC. Choi YM. Narasimhan S. Inorg. Chem. 1981, 20: 4454