靛红衍生物的不对称催化烯基化反应研究

不对称烯基化反应是构建Csp3-Csp2化学键的重要途径。目前报道的烯基化试剂有烯基硼试剂，烯基硅试剂，烯基金属试剂等。烯烃是最理想的烯基化试剂，但是它参与的不对称烯基化反应还很少有人报道。靛红及其衍生物是构建手性氧化吲哚的重要反应物，它们与烯烃的不对称烯基化反应可以合成结构新颖的手性3-烯基氧化吲哚化合物，但是这类化学转化还未见有人报道。本项目将研究在手性催化剂作用下，富电子烯烃3-烯基吲哚和苯乙烯与靛红、靛红亚胺以及靛红吲哚醇的不对称烯基化反应，建立靛红衍生物的不对称烯基化反应方法学；将烯基化产物应用到多环手性吲哚化合物和3-取代-3-甲酰基氧化吲哚衍生物的合成中；还研究3-取代-3-甲酰基氧化吲哚衍生物在合成天然化合物(+)-gliocladin C，TMC-95 A-D和(+)-chaetominine，以及合成子3α-amino-pyrroloindoline上的应用。

The asymmetric alkenylation reaction is an important strategy for the Csp3-Csp2 bond formation. The commonly used alkenylation reagents include alkenyl borons, alkenyl silicons and alkenyl metal compounds. In comparison, alkene is the most ideal alkenylation reagent because of its abundant resource and atom-economic reaction manner. However, the direct alkenylation reaction by alkene has rarely been reported. Isatin derivatives are important starting materials for the preparation of chiral oxindole compounds. The direct asymmetric alkenylation of isatin derivatives by alkenes, a good strategy for the synthesis of chiral 3-alkenyl oxindoles, has never been disclosed, yet. In this project, we will explore the catalytic asymmetric alkenylation of isatin derivatives, include the isatin, isatin imine and isatin derived 3-indolylmethanol, by 3-vinyl indole and styrene. We will also explore the application of the alkenylation products for the preparation of polycyclic chiral indole compounds, as well as the formal or total synthesis of (+)-gliocladin C，TMC-95 A-D, (+)-chaetominine and 3α-amino-pyrroloindoline.