Synthesis 2014; 46(01): 96-100
DOI: 10.1055/s-0033-1338577
paper
© Georg Thieme Verlag Stuttgart · New York

A Convenient Preparation of Thieno[3,2-c]pyrazole[1]

John Airey
,
Matthieu Barrague
,
Michael L. Edwards
,
Michael Ferro
,
Dirk Friedrich
,
Timothy A. Gillespy
,
John Jurcak
,
Kwon Musick
,
Philip M. Weintraub*
Weitere Informationen

Publikationsverlauf

Received: 08. August 2013

Accepted after revision: 03. Oktober 2013

Publikationsdatum:
28. November 2013 (online)


Abstract

A practical synthesis of multigram quantities of 1H-thi­eno[3,2-c]pyrazole is presented in which the Jacobson reaction serves as the key step.

 
  • References

  • 1 Heterocycles, part 14. For part 13, see: Weintraub PM. J. Heterocycl. Chem. 1993; 30: 1635
  • 2 Current address: Retired.
  • 3 Current address: Chemical Research, Sanofi US, 153 2nd Ave, Waltham, MA 02451, USA.
  • 4 Current address: 33 Casale Drive South, Warren, NJ 07059, USA.
    • 5a Görtz R, Appelboom T. Int. J. Tissue React. 1985; 7: 263
    • 5b Vinge E, Bjorkman SB. Acta Pharmacol. Toxicol. 1986; 59: 165
    • 6a Pinto DJ. P, Orwat MJ, Koch S, Rossi KA, Alexander RM, Smallwood A, Wong PC, Rendina AR, Luettgen JM, Knabb RM, He K, Xin B, Wexler RR, Lam PY. S. J. Med. Chem. 2007; 50: 5339
    • 6b Martin MT, Nutescu EA. Curr. Med. Res. Opin. 2011; 27: 2123
  • 7 Cui JJ, Tran-Dubé M, Shen H, Nambu M, Kung P.-P, Pairish M, Jia L, Meng J, Funk L, Botrous I, McTigue M, Grodsky N, Ryan K, Padrique E, Alton G, Timofeevski S, Yamazaki S, Li Q, Zhou H, Christensen J, Mroczkowski B, Bender S, Kania RS, Edwards MP. J. Med. Chem. 2011; 54: 6342
  • 8 Lin Q, Meloni D, Pan Y, Xia M, Rodgers J, Shepard S, Li M, Galya L, Metcalf B, Yue T.-Y, Liu P, Zhou J. Org. Lett. 2009; 11: 1999
  • 9 Gronowitz S, Westerlund C, Hörnfeldt AB. Chem. Scr. 1977; 12: 1
  • 10 Gronowitz S, Westerlund C, Hörnfeldt AB. Acta Chem. Scand., Ser. B 1975; 29: 224
  • 11 Colburn VM, Iddon B, Suschitzky H, Gallagher PT. J. Chem. Soc., Chem. Commun. 1978; 453
    • 12a Dell’Erba C, Novi M, Petrillo G, Tavani C. Tetrahedron 1992; 48: 325
    • 12b Dell’Erba C, Novi M, Petrillo G, Tavani C. Tetrahedron 1994; 50: 3529
    • 12c Fusco R, Marchesini A, Sannicolo F. J. Heterocycl. Chem. 1987; 24: 773
    • 13a Bartsch RA, Yang I.-W. J. Heterocycl. Chem. 1984; 21: 1063
    • 13b Hoegerle K, L’Écuyer P. Can. J. Chem. 1959; 37: 2068
    • 13c Benchidmi M, Bouchet P, Lazaro R. J. Heterocycl. Chem. 1979; 16: 1599
    • 13d Wrzeciono U, Dudinska-Usarewicz J, Majewska K, Stasieczko-Rydelkiewicz I, Stefanowicz J, Nieweglowska W. Pharmazie 1985; 40: 105
    • 13e Barbet O, Minjat M, Petavy A.-F, Paris J. Eur. J. Med. Chem. 1986; 21: 359
    • 13f Kazimierczuk Z, Lönnberg H, Vilpo J, Pfleiderer W. Nucleosides Nucleotides 1989; 8: 599
    • 13g Sun J.-H, Teleha CA, Yan J.-S, Rodgers JD, Nugiel DA. J. Org. Chem. 1997; 62: 5627
    • 13h Arnautu A, Collot V, Ros JC, Alayrac C, Witulski B, Rault S. Tetrahedron Lett. 2002; 43: 2695
    • 13i Forbes IT, Douglas S, Gribble AD, Ife RJ, Lightfoot AP, Garner AE, Riley GJ, Jeffrey P, Stevens AJ, Stean TO, Thomas DR. Bioorg. Med. Chem. Lett. 2002; 12: 3341
    • 14a Jacobson P, Huber L. Ber. Dtsch. Chem. Ges. 1908; 41: 660
    • 14b Huisgen R, Nakaten H. Justus Liebigs Ann. Chem. 1954; 586: 84
    • 14c Ruchardt C, Hassmann V. Liebigs Ann. Chem. 1980; 908
    • 15a Ockenen DW, Schofield K. J. Chem. Soc. 1953; 1915
    • 15b Huisgen R, Bast K. Org. Synth. Coll. Vol. V . Wiley; London: 1973: 650
    • 15c Ruchardt C, Hassmann V. Synthesis 1972; 375
    • 15d Forster HE, Hurst J. J. Chem. Soc., Perkin Trans. 1 1973; 2901
    • 15e Chapman D, Hurst J. J. Chem. Soc., Perkin Trans. 1 1980; 2398
    • 15f Pellegrin V, Fruchier A, Elguero J. J. Labelled Compd. 1981; 18: 999
    • 15g Bailey RJ, Card PJ, Shecter H. J. Am. Chem. Soc. 1983; 105: 6096
    • 15h Gueiffier A, Milhavet JC, Blache Y, Chavignon O, Teulade JC, Madesclaire M, Viols H, Dauphin G, Chapat JP. Chem. Pharm. Bull. 1990; 38: 2352
    • 15i Yoshida T, Matsuura N, Yamamoto K, Doi M, Morie T, Shimada T, Kato S. Heterocycles 1996; 43: 2701
    • 15j Mewshaw RE, Nelson JA, Shah US, Shi X, Mazandarani H, Coupert J, Marquis K, Brennen JA, Andree TH. Bioorg. Med. Chem. Lett. 1999; 9: 2593
    • 15k Miller RB, Stowell JG, Dugar S, Moock TE, Jenks CW, Farmer SC, Phan B, Wujcik CE, Olmstead MM. Tetrahedron 2002; 58: 6061
    • 15l Cui JJ, Araldi G.-L, Reiner JE, Reddy KM, Kemp SJ, Ho JZ, Siev DV, Mamedova L, Gibson TS, Gaudette JA, Minami NK, Anderson SM, Bradbury AE, Nolan TG, Semple JE. Bioorg. Med. Chem. Lett. 2002; 12: 2925
    • 15m Kourafalos VN, Marakos P, Pouli N, Terzis A, Townsend LB. Heterocycles 2002; 57: 2335
    • 15n Marakos P, Pouli N, Wise DS, Townsend LB. Synlett 1997; 561
    • 15o Wrobleski ST, Chen P, Hynes Jr J, Lin S, Norris DJ, Pandit CR, Spergel S, Wu H, Tokarski JS, Chen X, Gillooly KM, Kiener PA, McIntyre KW, Patil-koota V, Shuster DJ, Turk LA, Yang G, Leftheris K. J. Med. Chem. 2003; 46: 2110
    • 16a Nystrom RF. J. Am. Chem. Soc. 1959; 81: 610

    • For similar alane reductions, see also:
    • 16b Wigfield DC, Taymaz K. Tetrahedron Lett. 1973; 4841
    • 16c Tucker H. J. Med. Chem. 1980; 23: 1122
  • 17 Moody CJ, Shah P. J. Chem. Soc., Perkin Trans. 1 1989; 2463
  • 18 Fuller LS, Iddon B, Smith KA. J. Chem. Soc., Perkin Trans. 1 1997; 3465
  • 19 An aliquot was removed and worked up by filtration, concentration of the filtrate, and chromatography of the residue. Combination and concentration of amide-containing fractions gave N-(2-methyl-3-thienyl)acetamide as a light-beige solid. 1H NMR: δ = 2.18 (s, 3 H), 2.31 (s, 3 H), 7.01 (d, 1 H), 7.27 (d, 1 H). 13C NMR: δ = 12.25, 23.73, 120.69, 124.34, 126.10, 131.49, 167.84. Anal. Calcd for C7H9NOS: C, 54.17; H, 5.84; N, 8.78; S, 20.66. Found: C, 53.92; H, 5.86; N, 8.78; S, 20.51.
  • 20 Although the Jacobson reaction has been shown to yield a mixture of N 1-acetyl and N 2-acetyl tautomers, we never obtained any of the N 2-acetyl material.
  • 21 Gronowitz S, Moses P, Hörnfeld A.-B, Hakansson R. Ark. Kemi 1961; 17: 165