Synlett 2013; 24(7): 891-892
DOI: 10.1055/s-0032-1318499
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© Georg Thieme Verlag Stuttgart · New York

Dialkylaminodifluorosulfinium Salts: XtalFluor-E and XtalFluor-M

Antonio Franconetti
Departamento de Química Orgánica, Facultad de Química, Universidad de Sevilla, Apartado de Correos No. 1203, 41071 Sevilla, Spain   Email: afranconetti@us.es
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Further Information

Publication History

Publication Date:
19 March 2013 (eFirst)

Introduction

Fluorination is an important reaction in medicinal chemistry.[1] Fluorinated analogues of biomolecules frequently show increased biological power, lipidic permeability and metabolic stability. Diethylaminosulfur trifluoride (DAST) has been widely used for directly replacing a hydroxyl group by fluorine under very mild conditions.[2] [3] Nevertheless, the corrosive properties of DAST make it unsuitable for high-scale usage.

In this context, commercially available aminodifluorosulfinium salts,[4] such as XtalFluor-E (1) or XtalFluor-M (2), are efficient alternatives. These fluorinating agents are crystalline, more selective and significantly more stable[5] than Deoxo-Fluor or DAST and do not react violently with water.[6]

Reaction of DAST with tetrafluroboric acid provides, by elimination of HF, diethylaminodifluorosulfinium tetrafluoroborate 1 in excellent yield (Scheme [1]).[5]

Zoom Image
Scheme 1
 
  • References

  • 1 Kirk KL. Org. Process Res. Dev. 2008; 12: 305
  • 2 Ferret H, Déchamps I, Gomez-Pardo D, Van Hijfte L, Cossy J. Arkivoc 2010; (viii): 126
    • 3a Borrachero P, Cabrera-Escribano F, Carmona-Asenjo A, Gómez-Guillén M. Tetrahedron: Asymmetry 2000; 11: 2927
    • 3b Vera-Ayoso Y, Borrachero P, Cabrera-Escribano F, Carmona-Asenjo A, Gómez-Guillén M. Tetrahedron: Asymmetry 2004; 15: 429
    • 3c Vera-Ayoso Y, Borrachero P, Cabrera-Escribano F, Gómez-Guillén M, Vogel P. Synlett 2006; 45
    • 3d Vera-Ayoso Y, Borrachero P, Cabrera-Escribano F, Gómez-Guillén M, Carner J, Farrás J. Synlett 2010; 271
  • 4 Markovskii LN, Pashinnik VE, Saenko EP. Zh. Org. Khim. 1977; 13: 1116
  • 5 L`Heureux A, Beaulieu F, Bennett C, Bill DR, Clayton S, LaFlemme F, Mirmehrabi M, Tadayon S, Tovell D, Couturier M. J. Org. Chem. 2010; 75: 3401
  • 6 Nemoto H, Tabuko K, Shimizu K, Akai S. Synlett 2012; 23: 1978
  • 7 Pouliot M.-F, Mahé O, Hamel J.-D, Desroches J, Paquin J.-F. Org. Lett. 2012; 14: 5428
  • 8 Beaulieu F, Beuregard LP, Courchesne G, Couturier M, LaFlemme F, L´Heureux A. Org. Lett. 2009; 11: 5050
  • 9 Srinivasarao M, Park T, Chen Y, Fuchs P. Chem. Commun. 2011; 5858
  • 10 Tsegay S, Williams RJ, Williams SJ. Carbohydr. Res. 2012; 357: 16
  • 11 Cochi A, Gomez PardoD, Cossy J. Org. Lett. 2011; 13: 444
  • 12 Pouliot M.-F, Angers L, Hamel J.-D, Paquin J.-F. Org. Biomol. Chem. 2012; 10: 988
  • 13 Pouliot M.-F, Angers L, Hamel J.-D, Paquin J.-F. Tetrahedron Lett. 2012; 53: 4121
  • 14 Orliac A, Gomez Pardo D, Bombrun A, Cossy J. Org. Lett. 2013; 15: 902