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DOI: 10.1055/s-0034-1380501
1,1,2,2,3,3,4,4,4-Nonafluorobutane-1-sulfonyl fluoride (NfF)
Publikationsverlauf
Publikationsdatum:
27. Mai 2015 (online)
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Introduction
1,1,2,2,3,3,4,4,4-Nonafluorobutane-1-sulfonyl fluoride (NfF) is a versatile compound in organic synthesis. It can be used as a fluoride source for the nucleophilic introduction of fluorine,[1] but it is also frequently applied as sulfonylation reagent generating intermediates with strong electron-withdrawing perfluorinated alkyl substituents.[2]
NfF is produced on industrial scale by anodic fluorination of sulfolene (1, Scheme [1]),[3] therefore it is a fairly cheap reagent and commercially available from several suppliers. The compound is bench-stable and storable for years, non-toxic and easy to handle.
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(A) NfF can be used as a convenient fluoride source for the nucleophilic introduction of fluorine via the corresponding O-nonaflate as demonstrated by Vorbrüggen.[4] The application of this method on industrial scale was demonstrated for the synthesis of iodenosine by Takamatsu et al.[5] |
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(B) NfF is also a common sulfonylating agent that allows the conversion of carbonyl compounds 2, their corresponding trimethylsilyl enol ethers or phenol derivatives 3 into nonaflates.[6] These alkenyl and aryl nonaflates are efficient precursors for all kinds of cross-coupling reactions, in which they often show a better reactivity and a superior stability during transformations than the related tosylates or triflates.[7] |
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(C) The elimination of in situ formed alkenyl nonaflates derived from aldehydes or ketones in the presence of P-base gives terminal alkyne intermediates 4, as reported by Lyapkalo and Vogel in their one-pot synthesis of enynes 5.[8] This synthetically useful method was later successfully applied by Huwyler and Carreira in their total synthesis of the chlorinated sesquiterpene (±)-gomerone C,[9] or by Nicolaou et al. for the preparation of the cytotoxic polyketides myceliothermophins E, C and D.[10] |
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(D) Furthermore, NfF is also a powerful reagent in numerous nucleophilic displacement reactions under very mild reaction conditions. The intermediate nonaflates undergo intramolecular substitutions leading to useful compounds such as epoxides 6 (X = O),[11] aziridines 6 (X = NTs) or thiazolines 7.[12] |
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(E) Another interesting application of NfF involves its reaction with sodium azide, smoothly forming nonafluorobutane sulfonyl azide 8.[13] This azide is a stable liquid at room temperature and therefore easier and safer to handle than the corresponding trifluoromethane sulfonyl azide. The compound was used for Cu(II)-catalyzed diazo transfer reactions furnishing organic azides (R = alkyl or aryl).[14] |
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References
- 1 Vorbrüggen H. Synthesis 2008; 1165
- 2 Zimmer R, Webel M, Reissig H.-U. J. Prakt. Chem. 1998; 340: 274
- 3 Beyl V, Niederprüm H, Voss P. Liebigs Ann. Chem. 1970; 731: 58
- 4 Bennua-Skalmowski B, Vorbrüggen H. Tetrahedron Lett. 1995; 36: 2611
- 5 Takamatsu S, Katayama S, Hirose N, De Cock E, Schelkens G, Demillequand M, Brepoels J, Izawa K. Nucleosides Nucleotides 2002; 21: 849
- 6 Hirsch E, Hünig S, Reissig H.-U. Chem. Ber. 1982; 115: 3687
- 7 Högermeier J, Reissig H.-U. Adv. Synth. Catal. 2009; 351: 2747
- 8 Lyapkalo IM, Vogel MA. K. Angew. Chem. Int. Ed. 2006; 45: 4019
- 9 Huwyler N, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 13066
- 10 Nicolaou KC, Shi L, Lu M, Pattanayak MR, Shah AA, Ioannidou HA, Lamani M. Angew. Chem. Int. Ed. 2014; 53: 10970
- 11 Klar U, Neef G, Vorbrüggen H. Tetrahedron Lett. 1996; 37: 7497
- 12 Yan Z, Guan C, Yu Z, Tian W. Tetrahedron Lett. 2013; 54: 5788
- 13 Zhu S.-Z. J. Chem. Soc., Perkin Trans. 1 1994; 2077