Synlett 2015; 26(17): 2336-2350
DOI: 10.1055/s-0034-1378804
account
© Georg Thieme Verlag Stuttgart · New York

Diversity in Synthesis of N-Heterocycles from Simple Propargylic Alcohols

Eric Gayon
a   Institut Charles Gerhardt, UMR 5253 CNRS-UM2-UM1-ENSCM, 8 rue de l’École Normale, 34296 Montpellier Cedex 5, France   Email: emmanuel.vrancken@enscm.fr   jean-marc.campagne@enscm.fr
,
Hélène Gerard
b   Laboratoire de Chimie Théorique, UMR 7616, UPMC—Université Paris 06, CNRS case 137, 4 Place Jussieu, 75262 Paris Cedex 05, France
,
Emmanuel Vrancken*
a   Institut Charles Gerhardt, UMR 5253 CNRS-UM2-UM1-ENSCM, 8 rue de l’École Normale, 34296 Montpellier Cedex 5, France   Email: emmanuel.vrancken@enscm.fr   jean-marc.campagne@enscm.fr
,
Jean-Marc Campagne*
a   Institut Charles Gerhardt, UMR 5253 CNRS-UM2-UM1-ENSCM, 8 rue de l’École Normale, 34296 Montpellier Cedex 5, France   Email: emmanuel.vrancken@enscm.fr   jean-marc.campagne@enscm.fr
› Author Affiliations
Further Information

Publication History

Received: 23 March 2015

Accepted after revision: 15 June 2015

Publication Date:
01 September 2015 (online)


Abstract

In this account, we summarize our recent work on the preparation of various N-heterocycles, starting from propargylic alcohols. Our aim was to develop versatile and selective one-pot procedures that would permit the synthesis of large collections of heterocycles, such as di- or tri-substituted isoxazolines and isoxazoles, cis-aziridines, and pyrimidines, by fine changes in the reaction conditions. When needed, mechanistic studies have been performed by combining experimental work with density functional theory calculations.

1 Introduction

2 Synthesis of Disubstituted Isoxazolines

3 Synthesis of Disubstituted Isoxazoles

4 Synthesis of cis-Acylaziridines

5 Trisubstituted Isoxazolines and Isoxazoles

6 β-Enaminones and Pyrimidines

7 Conclusion

 
  • References

    • 1a Vitaku E, Smith DT, Njardarson JT. J. Med. Chem. 2014; 57: 10257
    • 1b Modern Heterocyclic Chemistry. Alvarez-Builla J, Vaquero JJ, Barluenga J. Wiley-VCH; Weinheim: 2011
    • 2a Georgy M, Boucard V, Debleds O, Dal Zotto C, Campagne J.-M. Tetrahedron 2009; 65: 1758
    • 2b Debleds O, Gayon E, Vrancken E, Campagne JM. Beilstein J. Org. Chem. 2011; 7: 866
  • 3 Georgy M, Boucard V, Campagne J.-M. J. Am. Chem. Soc. 2005; 127: 14180

    • For reviews, see:
    • 4a Miyake Y, Uemura S, Nishibayashi Y. ChemCatChem 2009; 1: 342
    • 4b Detz RJ, Hiemstra H, van Maarseveen JH. Eur. J. Org. Chem. 2009; 6263
    • 4c Bauer EB. Synthesis 2012; 44: 1131
  • 5 Debleds O, Dal Zotto C, Vrancken E, Campagne J.-M, Retailleau P. Adv. Synth. Catal. 2009; 351: 1991

    • For the later use of biprotected hydrazines in these reactions, see:
    • 6a Yoshimatsu M, Ohta K, Takahashi N. Chem. Eur. J. 2012; 18: 15602
    • 6b Xu S.-x, Hao L, Wang T, Ding Z.-C, Zhan Z.-p. Org. Biomol. Chem. 2013; 11: 294
  • 7 Zhan Z.-p, Yu J.-l, Liu H.-j, Cui Y.-y, Yang R.-f, Yang W.-z, Li J.-p. J. Org. Chem. 2006; 71: 8298
  • 8 Ji W.-h, Pan Y.-m, Zhao S.-y, Zhan Z.-p. Synlett 2008; 3046
  • 9 Aschwanden D, Frantz DE, Carreira EM. Org. Lett. 2000; 2: 2331
  • 10 Debleds O, Gayon E, Ostaszuk E, Vrancken E, Campagne JM. Chem. Eur. J. 2010; 16: 12207
  • 11 Dal Zotto C, Michaux J, Zarate-Ruiz A, Gayon E, Virieux D, Campagne J.-M, Terrasson V, Pieters G, Gaucher A, Prim D. J. Organomet. Chem. 2011; 696: 296
  • 12 Baldwin JE, Pudussery RG, Qureshi AK, Sklarz B. J. Am. Chem. Soc. 1968; 90: 5325
  • 13 Ishikawa T, Kudoh T, Yoshida J, Yasuhara A, Manabe S, Saito S. Org. Lett. 2002; 4: 1907
  • 14 Gayon E, Debleds O, Nicouleau M, Lamaty F, van der Lee A, Vrancken E, Campagne JM. J. Org. Chem. 2010; 75: 6050
  • 15 Robiette R. J. Org. Chem. 2006; 71: 2726
  • 16 For a review, see: Kappe CO. Angew. Chem. Int. Ed. 2004; 43: 6250
  • 17 Pinho e Melo TM. V. D. Curr. Org. Chem. 2005; 9: 925
    • 18a Waldo JP, Larock RC. Org. Lett. 2005; 7: 5203
    • 18b Waldo JP, Larock RC. J. Org. Chem. 2007; 72: 9643
    • 18c Crossley JA, Browne DL. J. Org. Chem. 2010; 75: 5414
    • 18d Waldo JP, Metha S, Neuenswander B, Lushington GH, Larock RC. J. Comb. 2008; 10: 658
    • 18e Okitsu T, Potewar TM, Wada A. J. Org. Chem. 2011; 76: 3438
  • 19 Arcadi A, Cacchi S, Del Rosario M, Fabrizi G, Marinelli F. J. Org. Chem. 1996; 61: 9280
  • 20 Hu Y, Nawoschik KJ, Liao Y, Ma J, Fathi R, Yang Z. J. Org. Chem. 2004; 69: 2235
  • 21 Gayon E, Quinonero O, Lemouzy S, Vrancken E, Campagne J.-M. Org. Lett. 2011; 13: 6418
  • 22 Guinchard X, Vallée Y, Denis J.-N. Org. Lett. 2005; 7: 5147
  • 23 Gayon E, Szymczyk M, Gérard H, Vrancken E, Campagne JM. J. Org. Chem. 2012; 77: 9205

    • For selected recent publications on the synthesis of pyrimidines, see:
    • 24a Hill MD, Movassaghi M. Chem. Eur. J. 2008; 14: 6836
    • 24b Lin M, Chen Q.-z, Zhu Y, Chen X.-l, Cai J.-j, Pan Y.-m, Zhan Z-p. Synlett 2011; 1179
    • 24c Duerfeldt AS, Boger DL. J. Am. Chem. Soc. 2014; 136: 2119