1、硫被氟取代合成氟化合物

       和氧一样，含硫化合物如硫醇，硫缩酮，硫缩醛以及硫羰基化合物在氟代试剂的作用下，碳硫键断裂，硫原子被氟取代，生成相应的氟化物。这个方法于 1976 年由Kollonitsch和Marburg首次报导。和氧相比，硫更容易被取代。常用的试剂包括HF/CF3OF，HF/F2 ，HF/Pyridine，Bu4NH2F3，Tol-IF2，SF4，FBr3，MoF6和DAST等。

      硫醇被氟取代生成相应的一氟代化合物:

       而硫缩酮和硫缩醛则生成二氟代化合物，如果底物含有对酸敏感的基团,Bu4NH2F3是很好的替代方法。

Tol-IF2也能在温和地的条件下高产率的取代硫缩酮.

      硫羰基化合物，如硫酰氯，硫酯等经HF/Pyridine，Bu4NH2F3 ，MoF6 或DAST处理，也生成氟代化合物 

反应示例

    To a solution of thioester (1.58 g, 10 mmol) in dry CH2Cl2 (20 mL) was dropped DAST in CH2Cl2 (1M, 20 mL, 20 mmol) at room temperature under nitrogen atmosphere. The reaction mixture was stirred for 6 h, and then quenched by addition of saturated NaHCO3 (30mL). The organic layer was separated, and the aqueous phase was extracted with CH2Cl2 . The combined organic layer was dried over Na2SO4 , concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to give the desired product (1.32 g, 81%).

2、磺酸酯被氟取代合成氟化合物

      磺酸酯，如甲磺酸酯，对甲苯磺酸酯在极性非质子溶剂（DMF，CH3CN, DMSO等）中与碱金属氟化物发生亲核取代反应，得到氟化合物。

      碱金属氟化物在非质子溶剂中活性如下：CsF>KF>NaF>LiF。CsF 的活性最高，但由于 KF 价格相对便宜，所以最常用。

      反应体系中加入冠醚等相转移催化剂会加快反应进行，提高产率。

      有的底物在离子液体中进行反应，能得到很好得结果。如下这个反应在离子液体[bmim]BF 4 中进行，产率相当高。

黄原酸酯也能被取代生成氟化物

反应示例

  CsF (760 mg, 5 mmol) was added to the mixture of 2-(3-methanesulfonyloxypropyl) naphthalene (264 mg, 1.0 mmol), [bmim]-[BF4] (3.0 mL), and H2O (90 íL, 5 mmol) in acetonitrile (3.0 mL). The mixture was stirred at 100 °C for 20 min. The reaction was monitored by TLC. The reaction mixture was extracted from the ionic liquid phase with ethyl ether (7mL× 3). The ether layer was dried over Na 2 SO 4 and evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel (5%EtOAc/hexane) to give 2-(3-fluoropropyl)naphthalene (179 mg , 95%) as a colorless oil.