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在杂原子酸烯丙酯和低价过渡金属配合物反应的系统研究中,我们发现在四(三苯膦)钯韵催化下,亚磺酸烯丙酯能够容易地重排成相应的砜.反应温度要比相应的热重排低得多,而且时间短,产率高. 重排反应的典型实例如下:在25℃氩气气氛下,向溶有91mg(0.5mmol)苯基亚磺酸烯丙基酯(1a)的5mL四氢呋喃溶液中加入25mg(0.022mmol)四(三苯膦)钯,搅拌反应混合物,薄层层析跟踪直至原料消失,耗时约70分钟.减压除去四氢呋喃,残渣用四氯化碳萃取,硅胶制备薄层层析分离[5:1石油醚(30～60℃)-乙酸乙酯],得79mg油状物,产率87％,b.p.130℃(浴温)/0.2 mm(文献值:111～113℃/0.25mm).结果如表1所示.
In a systematic study of the reaction of heteroatomic allyl esters with low-valent transition metal complexes, we found that the allyl sulfinate can be readily rearranged to the corresponding sulfone under palladium (III) tetrakis (triphenylphosphine) palladium ruthenium. The reaction temperature is much lower than the corresponding thermal rearrangement, and the time is short and the yield is high Typical examples of the rearrangement reaction are as follows: To a solution of 91 mg (0.5 mmol) of phenylsulfinic acid Of allyl ester (1a) in 5 mL of tetrahydrofuran was added 25 mg (0.022 mmol) of tetrakis (triphenylphosphine) palladium and the reaction mixture was stirred and the layer was chromatographed until the starting material disappeared in approximately 70 minutes.The tetrahydrofuran was removed under reduced pressure, The residue was extracted with carbon tetrachloride and chromatographed on silica gel [5: 1 petroleum ether (30-60 ° C) -ethyl acetate] to give 79 mg of an oil in 87% yield, bp 130 ° (bath temperature) /0.2mm (literature value: 111 ~ 113 ℃ / 0.25mm) The results are shown in Table 1.