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三氟甲磺酰衍生物

1992年,Langlois報(bào)道了在Cu(OTf)2的存在下,CF3SO2Na和t-BuO2H發(fā)生單電子氧化產(chǎn)生的親電性的三氟甲基自由基和烯醇醋酸酯的反應(yīng)1。

反應(yīng)實(shí)例:

In a typical procedure, 7.8 mL of 63% aqueous t-BuOOH(50 mmol) were dropped at room temperature, within 100 min by the mean of a syringe pump, onto a solution of STM. (10 mmol), CF3SO2Na(10 mmol) and Cu(OSO2CF3)2 (2.5 mmol) in acetonitrile (30 mL). After standing at room temperature for 2.5 h then treatment with aqueous sodium metabisulfite, an oily layer was separated. The remaining solution was extracted with petroleum ether (3×30 mL). The organic phases were gathered, dried and evaporated. The products were separated by column chromatography on silica.    


三氟甲磺酰氯被用于在RuCl2(PPh3)3的存在下將三氟甲基引入到烯烴,芳烴和烯醇硅醚2。

反應(yīng)實(shí)例2b

General Procedure for the Reaction of Perfluoroalkanesu1phonyl Chlorides with Alkenes.

A solution containing a perfluoro alkanesulphonyl chloride (2.0 mmol), alkene (4-10 mmol), and dichlorotris(triphenylphosphine)ruthenium(II) (0.02mmol) in dry benzene (4 mL) was degassed by a freeze-pump-thaw cycle, sealed in an ampoule, and heated at 120 oC for 24 h. The reaction mixture was subjected to short-column chromatography on Florisil with benzene as eluent to remove the metal complex. The products were isolated from the reaction mixture by the use of gel-permeation chromatography and/or column chromatography oversilica gel.

【參考文獻(xiàn)】

1. Langlois, B. R.; Laurent, E.; Roidot,N. Tetrahedron Lett. 1992, 33, 1291-1294.

2. (a) Kamigata, N.; Udodaira, K.; Shimizu, T. Phos. Sulfur Silicon Relat.Elem. 1997,   129, 155-168.

 (b) Kamigata, N.; Fukushima, T.; Terakawa, Y.; Yoshida, M.; Sawada, H. J.Chem.    Soc., Perkin Trans. 1991,1, 627-633.


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