An Easy Access to 4,5-Disubstituted Thiazoles via Base-Induced Click Reaction of Active Methylene Isocyanides with Methyl Dithiocarboxylates

Abstract

An efficient synthesis of 4,5-disubstituted thiazoles via base-induced cyclization of active methylene isocyanides such as tosylmethyl isocyanide, ethyl isocyanoacetate, and arylmethyl isocyanides with methyl arene- and hetarenecarbodithioates is reported. This synthesis could be a new click chemistry reaction, since it is simple, rapid, and often avoids purification steps. In addition, this method allow us a clear and general synthesis of novel 4,5-diarylthiazoles.

Keywords

thiazole - isocyanide - cyclization - dithioester - click reaction

• References

• 1 Tsuji K, Ishikawa H. Bioorg. Med. Chem. Lett. 1994; 4: 1601
• 2a Haviv F, Ratajczyk JD, DeNet RW, Kerdesky FA, Walters RL, Schmidt SP, Holms JH, Young PR, Carter GW. J. Med. Chem. 1988; 31: 1719
• 2b Miwatashi S, Arikawa Y, Kotani E, Miyamoto M, Naruo KI, Kimura H, Yanaka T, Asahi S, Ohkawa S. J. Med. Chem. 2005; 48: 5966
• 2c Papadopoulou C, Geronikaki A, Hadjipavlou-Litina D. Farmaco 2005; 60: 969
• 3a Patt WC, Hamilton HW, Taylor MD, Ryan MJ, Taylor DG. Jr, Connolly CJ. C, Doherty AM, Klutchko SR, Sircar I, Steinbaugh BA, Batley BL, Painchaud CA, Rapundalo ST, Michniewicz BM, Olson SC. J. J. Med. Chem. 1992; 35: 2562
• 3b Tsuruni Y, Ueda H, Hayashi K, Takase S, Nishikawa M, Kiyoto S, Okuhara M. J. Antibiot. 1995; 48: 1066
• 4 Bell FW, Cantrell AS, Hoegberg M, Jaskunas SR, Johansson NG, Jordan CL, Kinnick MD, Lind P, Morin JM. Jr, Noveen R, Oberg B, Palkowitz JA, Parrish CA, Pranc P, Sahlberg C, Ternansky RJ, Vasileft RT, Vrang L, West SJ, Zhang H, Zhou X.-Y. J. Med. Chem. 1995; 38: 4929
• 5a Kumar Y, Green R, Borysko KZ, Wise DS, Wotring LL, Townsend LB. J. Med. Chem. 1993; 36: 3843
• 5b Ei-Subbagh HI, Al-Obaid AM. Eur. J. Med. Chem. 1996; 31: 1017
• 6 Pereira R, Gaudon C, Iglesias B, Germain P, Gronemeyer H, de Lera AR. Bioorg. Med. Chem. Lett. 2006; 16: 49
• 7 Breslow R. J. Am. Chem. Soc. 1958; 80: 3719

For reviews, see:
• 8a Lygin AV, de Meijere A. Angew. Chem. Int. Ed. 2010; 49: 9094
• 8b Sadjadi S, Heravi MM. Tetrahedron 2011; 67: 2707
• 9a Wildeman J, van Leusen AM. Synthesis 1979; 733
• 9b Schöllkopf U, Porsch P, Blume E. Justus Liebigs Ann. Chem. 1976; 11: 2122
• 9c Hartman GD, Weinstock LM. Synthesis 1976; 681
• 9d Suzuki M, Moyira T, Matsumoto K, Miyoshi M. Synthesis 1982; 874
• 9e van Nipsen SP. J. M, Bregman JH, van Engen DG, van Leusen AM, Saikachi H, Kitagawa T, Sasaki H. Recl. Trav. Chim. Pays-Bas 1982; 101: 28
• 9f Oldenziel OH, van Leusen AM. Tetrahedron Lett. 1972; 13: 2777
• 9g Yamada M, Fukui T, Nunami K.-i. Tetrahedron Lett. 1995; 26: 257
• 10 Hantzsch A, Weber JH. Ber. Dtsch. Chem. Ges. 1887; 20: 3118
• 11 Cook AH, Heilbron I, MacDonald SF, Mahadevan AP. J. Chem. Soc. 1949; 1064
• 12 Metzger JV In Comprehensive Heterocyclic Chemistry . Vol. 6. Katritzky R, Rees CW. Pergamon; Oxford: 1984: 235
• 13a Martin LM, Hu BH. Tetrahedron Lett. 1999; 40: 7951
• 13b You SL, Kelly JW. J. Org. Chem. 2003; 68: 9506
• 14 Kazmaier U, Ackermann S. Org. Biomol. Chem. 2005; 3: 3184
• 15 Sasmal PK, Sridhar S, Iqbal J. Tetrahedron Lett. 2006; 47: 8661
• 16 Sheldrake PW, Matteucci M, McDonald E. Synlett 2006; 460
• 17 Castagnonlo D, Pagano M, Bernardini M, Botta M. Synlett 2009; 2093
• 18 Sanz-Cervera JF, Blasco R, Piera J, Cynaman M, Ibanez I, Fustero S. J. Org. Chem. 2009; 74: 8988
• 19a Narender M, Reddy MS, Kumar VP, Srinivas RS, Nageswar YV. D, Rao KR. Synthesis 2007; 3469
• 19b Mustafa SM, Nair VA, Chittoor JP, Krishna PS. Mini-Rev. Org. Chem. 2004; 1: 375
• 19c Wardakhan WW, Elkholy YM. Phosphorus, Sulfur, Silicon Relat. Elem. 2002; 177: 2661
• 19d Hermitage SA, Cardvell KS, Chapman T, Cooke JW. B, Newton R. Org. Process Res. Dev. 2001; 5: 37
• 20a Chandrappa S, Vinaya K, Ananda Kumar CS, Rangappa KS. Tetrahedron Lett. 2010; 51: 6493
• 20b Raghavendra GM, Ramesha AB, Revanna CN, Nandeesh KN, Mantelingu K, Rangappa KS. Tetrahedron Lett. 2011; 52: 5571
• 20c Chandrappa S, Vinaya K, Umashankara M, Rangappa KS. Tetrahedron Lett. 2011; 52: 5474
• 21 Ramadas SR, Srinivasan PS, Ramachandran J, Sastry VV. S. K. Synthesis 1983; 605 ; and references cited therein
• 22 Davies JR, Kane PD, Moody CJ. Tetrahedron 2004; 60: 3967
• 23 Jacobsen EJ, Stelzer LS, Belonga KL, Carter DB, Im WB, Sethy VH, Tang AH, VonVoigtlander PF, Petke JD. J. Med. Chem. 1996; 39: 3820