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联烯酸酯是近年来研究较多的一类重要的缺电子联烯,具有丰富的化学反应.本文着重总结了近年来在叔膦参与下(催化或化学计量方式)联烯酸酯与醛的新反应,包括2,3-丁二烯酸酯与醛的成环反应、γ-取代联烯酸酯与醛的[3+2]环加成反应和烯化反应、α-取代联烯酸酯与醛的Vinylogous Wittig反应以及环丙烷化反应,并从反应机理的角度,探讨了联烯酸酯与亲电试剂活化烯、亚胺和醛在反应性上的差异.在这些重要的化学转化中,叔膦的特殊性质如亲核性与夺氧能力起了关键的作用.
Bienoate is a kind of important electron-deficient diene, which has been researched more and more in recent years, and has abundant chemical reactions.In this paper, we summarize the recent progress of the coupling reaction of allenic acid esters with aldehydes (catalyzed or stoichiometric) Including the ring-forming reaction of 2,3-butadienoate with aldehydes, the [3 + 2] cycloaddition reaction and alkenylation of γ-substituted alicyclic acid esters with aldehydes, the reaction of α-substituted alkenes Vinylogous Wittig reaction and cyclopropanation reaction of the ester and aldehyde, and from the perspective of the reaction mechanism, the difference in reactivity between the alkene acid ester and the electrophile activated alkene, imine and aldehyde was discussed.In these important chemical In the conversion, the special properties of tertiary phosphines such as nucleophilicity and oxygen abstraction play a key role.