Fluorobis(phenylsulfonyl)methane: A fluoromethide equivalent and palladium-catalyzed enantioselective allylic monofluoromethylation
Fluorobis(phenylsulfonyl)methane: A fluoromethide equivalent and palladium-catalyzed enantioselective allylic monofluoromethylation
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DOI：
10.1002/anie.200600625
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Toru, Takeshi
中科院分区：
文献类型：
--
作者：
Fukuzumi, Takeo;Shibata, Norio;Toru, Takeshi
方法：在NaH(60%油性分散剂，270 mg，6.75 mm ol)的搅拌悬浮液中，加入市售的25 m l四氢呋喃，在0℃，氮气气氛下，加入二(苯磺酰基)甲烷(2.00 g，6.75 m ol)。在室温下搅拌30min后，在0℃下加入2.39g、6.75 mmol的Selectfluor-5ml的MeCN溶液，在室温下搅拌3h。通过加入饱和氯化铵水溶液使反应熄灭。然后用二氯甲烷提取混合物，用盐水洗涤，然后用无水Na2SO4烘干。溶剂挥发后，以2：8正己烷/二氯甲烷为洗脱剂，硅胶柱层析净化残留物，得到1(1.28g，60%)为无色针状物。方法：在氮气气氛下，在0℃下，将60%油分散剂NaH(110 mg，2.75 mmol)在THF(10ml)中搅拌后，加入二(苯磺酰基)甲烷(500 mg，1.69 mmol)。在室温下搅拌30min后，减压脱除溶剂。在残渣中加入17毫升的乙腈，将混合物冷却到-40℃，在氮气中小心地将10%F2气体通过溶液鼓泡2分钟。通过加入饱和的碳酸氢钠使反应熄灭。然后用二氯甲烷提取混合物，用盐水洗涤，然后用无水Na2SO4烘干。溶剂挥发，残留物经硅胶柱层析纯化，以2：8正己烷/二氯甲烷为洗脱液，得到1(128 mg，24%)为无色针。
Method A: To a stirred suspension of NaH (60% oil dispersion, 270 mg, 6.75 mmol) in THF (25 ml) was added commercially available, bis (phenylsulfonyl) methane (2.00 g, 6.75 mmol) at 0 C under nitrogen atmosphere. After 30 min stirring at room temperature, a solution of Selectfluor (2.39 g, 6.75 mmol) in MeCN (5 ml) was added at 0 C, and the mixture was stirred for 3 h at room temperature. The reaction was quenched by addition of saturated aqueous ammonium chloride. The mixture was then extracted by dichloromethane, washed with brine, and dried over anhydrous Na2SO4. The solvent was evaporated and the residue was purified by silica gel column chromatography using 2: 8 hexane/dichloromethane as the eluent to give 1 (1.28 g, 60%) as colorless needles.Method B: To a stirred suspension of NaH (60% oil dispersion, 110 mg, 2.75 mmol) in THF (10 ml) was added bis (phenylsulfonyl) methane (500 mg, 1.69 mmol) at 0 C under nitrogen atmosphere. After 30 min stirring at room temperature, the solvent was removed under reduced pressure. MeCN (17 ml) was added to the residue, and the mixture was cooled to-40 C. Gaseous 10% F2 in N2 was carefully bubbled through a solution for 2 min. The reaction was quenched by addition of saturated sodium bicarbonate. The mixture was then extracted by dichloromethane, washed with brine, and dried over anhydrous Na2SO4. The solvent was evaporated and the residue was purified by silica gel column chromatography using 2: 8 hexane/dichloromethane as the eluent to give 1 (128 mg, 24%) as colorless needles.