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烯丙基化合物在钯配合物催化下和亲核试剂的反应,已发展成为有机合成中的有用方法,我们曾在烯丙基化合物经钯催化的反应活性研究中,发现亚磷酸酯也是一个中等活性的离去基团;并发现在四(三苯膦)钯的催化下,亚磺酸烯丙酯能顺利地重排成相应的砜。但用四(三苯膦)钯为催化剂和亚磷酸烯丙酯反应时,不能分离得重排产物;进一步研究发现:在双(环辛二烯)镍的催化下,亚磷酸烯丙酯能够重排成相应的膦酸酯,反应温度要比相应的热重排低得多,而且时间短,产率高。
Allylic compounds catalyzed by palladium complexes react with nucleophiles and have developed into useful methods in organic synthesis. We have found that phosphites are also moderately active in the palladium-catalyzed reactivity studies of allyl compounds It was found that under the catalysis of tetrakis (triphenylphosphine) palladium, the allylsulfinate can be successfully rearranged to the corresponding sulfone. However, when tetrakis (triphenylphosphine) palladium was used as catalyst and allyl phosphite was reacted, rearrangement products could not be isolated. Further studies showed that under the catalysis of bis (cyclooctadiene) nickel, allyl phosphite could Rearranged into the corresponding phosphonate, the reaction temperature is much lower than the corresponding heat rearrangement, and the time is short, the yield is high.