有机膦催化α-取代联烯反应进展

Advances in Phosphine-Organocatalyzed Reactions of α-Substituted Allenes

摘要: 近几十年来，有机膦催化联烯反应已被确定为构建各种分子的一类关键的有机催化转化。联烯酸酯作为有机合成中的重要砌块，在有机膦催化下，可以形成两性离子中间体，作为C1、C2、C3、C4合成子与贫电子烯烃、亚胺、醛、酮等化合物发生环加成反应。该类方法具有环境友好、不含金属、反应条件温和等优点，是合成各种杂环化合物的一种实用而有力的策略。其中，不同取代联烯能够作为不同偶极子参与环化反应，本论文综述了近十几年来关于膦催化α-取代联烯作为不同合成子参与环化反应的研究进展。

Abstract: In recent decades, organophosphine-catalyzed reactions of allenes have been established as a pivotal class of organocatalytic transformations for constructing diverse molecular architectures. Allenic esters, serving as important building blocks in organic synthesis, can form zwitterionic intermediates under organophosphine catalysis. These intermediates function as C1, C2, C3, or C4 synthons to undergo cycloaddition reactions with electron-deficient alkenes, imines, aldehydes, ketones, and related compounds. This methodology offers significant advantages, including environmental benignity, metal-free conditions, and mild reaction parameters, rendering it a practical and powerful strategy for synthesizing various heterocyclic compounds. Notably, differentially substituted allenes can participate in cyclizations as distinct dipoles. This review summarizes the research progress over the last decade concerning the use of phosphine-catalyzed α-substituted allenes as versatile synthons in cyclization reactions.