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Synlett 2012; 23(16): 2413-2415
DOI: 10.1055/s-0032-1317157
DOI: 10.1055/s-0032-1317157
letter
Synthesis of β-Fluoro Amides Using Partially Hydrated Nickel Difluoride as Fluorine Source
Further Information
Publication History
Received: 14 June 2012
Accepted after revision: 30 July 2012
Publication Date:
10 September 2012 (online)
![](https://www.thieme-connect.de/media/synlett/201216/lookinside/thumbnails/10.1055-s-0032-1317157-1.jpg)
Abstract
β-Fluoro amides were obtained from the reactions of activated aziridines with partially hydrated nickel difluoride (NiF2·nH2O, n <4) in good yields (47–82%) in the presence of tetra-n-butylammonium fluoride (20 mol%), while the non-activated aziridines did not react under the same conditions.
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References
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- 9 Typical Procedure for the Ring Opening of Aziridine with Partially Hydrated Nickel Difluoride: To a stirred solution of aziridine 1a (0.5 mmol) and partially hydrated nickel difluoride (NiF2·nH2O, n <4, 1.68 g, approx. 1 mmol) in i-PrOH (3.0 mL) was added Bu4NF (0.1 mmol), and the mixture was stirred at 90 °C until 1a was consumed (monitored by TLC). The mixture was filtered by short silica gel column and washed with CH2Cl2, then the solvent was removed in vacuum and the residue was purified by flash column chromatography on silica gel to yield 2a as a white amorphous solid. N-(2-Fluorocyclohexyl)-4-methylbenzenesulfonamide (2a): 82% yield; mp 95–96 °C (lit.5 95–97 °C). 1H NMR (600 MHz, CDCl3, 25 °C, TMS): δ = 1.22–1.26 (m, 4 H), 1.57–1.70 (m, 2 H), 2.01–2.13 (m, 2 H), 2.43 (s, 3 H), 3.17 (m, 1 H), 4.15, 4.25 (double multiplet, 2 J HF = 50.1 Hz, 1 H), 4.81 (d, J = 5.4 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 2 H), 7.76 (d, J = 8.4 Hz, 2 H). 19F NMR (600 MHz, CDCl3, 25 °C, CF3COOH): δ = –179.3. IR (KBr): 3302, 2951, 1598, 1327, 1163, 1091, 1045, 893, 816, 667, 572, 551 cm–1.