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介绍了我们小组最近有关原位生成的烯丙基磷叶立德与醛的化学反应性研究结果.在化学计量叔膦作用下,烯丙基碳酸酯或联烯酸酯经原位生成的烯丙基磷叶立德活性中间体,与醛发生高度立体选择性的三组分Wittig烯化反应和vinylogous Wittig烯化反应,该类反应为合成多取代1,3-二烯衍生物提供了简单、高效的新方法;在催化量叔膦作用下,γ-甲基联烯酸酯经烯丙基磷叶立德关键中间体与醛发生多个膦催化的环化反应,为五元、六元含氧杂环化合物的合成提供了原子经济性的方法.通过氘代实验和核磁跟踪等方法,对上述反应机理进行了初步探索.
The recent results of our group’s study on the chemical reactivity of the allylic phosphorus ylide with aldehydes generated in situ were investigated.According to the stoichiometry of the tertiary phosphine the allyl carbonate or allenate is converted in situ to allyl Phosphonium ylide active intermediates, highly stereoselective three-component Wittig olefination and vinylogous Wittig olefination with aldehydes, which provide a simple, efficient new method for the synthesis of polysubstituted 1,3-diene derivatives Methods: Under the action of catalytic amount of tertiary phosphine, several phosphine-catalyzed cyclization reactions of γ-methyldienoic acid ester with aldehydes, phosphorus ylides and aldehydes were carried out, which were five-membered, six-membered oxygenated heterocyclic compounds Provides a method of atomic economy.Through the deuterium experiments and NMR tracking methods, the above reaction mechanism was initially explored.