Lewis碱催化的α-胺基腈及氰醇的烯丙基官能团化反应研究及应用

Lewis Base-Catalyzed Allylic Alkylation of α-Amino Nitriles and Cyanohydrins and Synthetic Applications

对我们研究小组近几年在Lewis碱催化具有α-位氢的α-胺基腈类及氰醇类化合物与Morita-Baylis-Hillman(MBH)加合物立体选择性的烯丙基化反应方面取得的初步成果进行了小结.通过与MBH加合物的烯丙基取代反应,有效地构建了具有α-位季碳结构单元的多官能团腈类衍生物,而且基于此发展了一类非金属催化的烯烃分子内氰官能团化反应,构建了β-位有季碳结构单元的官能团化的腈类化合物.此外对影响反应的可能因素也做了讨论,提出了可能的反应机理.

This article summarized our recent progress in Lewis base-catalyzed the direct allylic substitutions of Mo-rita-Baylis-Hillman （MBH） adducts withα-amino nitriles and cyanohydrins bearing anα-hydrogen, which provided efficient access to functionalizedα-amino nitriles and cyanohydrins incorporating quaternary carbon centers. On the basis of these, a novel metal-free carbocyanation （alkenylcyanation and acylcyanation） approach to construct functionalized nitriles incorpo-ratingβ-quaternary carbon center has been developed. In addition, the several factors influencing these chemical transforma-tions are discussed, and the possible mechanism is proposed.