β,γ-不饱和α-酮酸酯在不对称催化中的应用

New Application of β,γ-Unsaturatedα-Ketoesters in Asymmetric Catalysis

β,γ-不饱和α-酮酸酯是一种多官能团的合成子,其1,2-双羰基的结构便于进行活化和手性控制,多个反应位点可以进行多样的反应设计.近20年来,许多手性路易斯酸催化剂和有机小分子催化剂被应用到β,γ-不饱和α-酮酸酯参与的不对称催化反应中,得到了各种光活性化合物.根据β,γ-不饱和α-酮酸酯中的β,γ-不饱和α-酰基共轭体系、碳碳双键及羰基三种不同的反应位点分类,对近几年来β,γ-不饱和α-酮酸酯在不对称催化中的应用进展进行综述.同时对存在的局限性和未来的发展趋势进行了展望.

β,γ-Unsaturatedα-ketoester is a class of polyfunctional synthon.Due to its 1,2-dicarbonyl structure and multiple reactive sites,it has been used for the synthesis of various compounds.In the past twenty years,a number of chiral Lewis acid catalysts and organocatalysts have been applied to asymmetric catalytic reactions usingβ,γ-unsaturatedα-ketoesters and various optically active compounds have been synthesized.The current progress ofβ,γ-unsaturatedα-ketoesters in asymmetric catalysis according to the three different reaction sites,unsaturated acyl conjugate system,carbon-carbon double bond and carbonyl group,is summarized.Finally,the limitation of related reactions and the future development trends are also pointed out.