氮杂半冠醚手性配体催化不对称合成3-取代-3-羟基氧化吲哚类化合物研究-有机化学专业论文.docx

Abst Abstract 万方数据 万方数据 Abstract In this thesis, we have committed ourselves to reaearch the asymmetric synthesis of 3-substituted-3-hydroxyoxindole catalyzed by the organometallic catalyst. The addition of isatins to hydrazine can go under mild condition and the scope of substrates is quite wide. Besides that, novel 3,3’-disubsituted oxindoles was prepared through derivatization of products. Thus we offer an efficient method to synthesize the 3,3’-disubsituted oxindoles. 3,3’-disubsituted oxindoles can be widely used for total synthesis of pharmaceuticals, so they get a lot of attention because of their potential application value. Therefore we developed the addition of formaldehyde tert–butyl hydrazone to isatins catalyzed by dinuclear zinc catalyst to synthesis chiral 3-substituted- 3-hydroxyoxindole. After that we optimized the experimental conditions such as catalyst, solvent, additive and temperature to improve yield and ee. It was found that at the optimal conditions the asymmetric addition can afford the products in good results (up to 98% yield, up to 97% ee). The scope of reaction was explored with a range of isatin derivatives most of which attained satisfactory results (90% yield, 90% ee). And a possible mechanism was proposed. Eventually, derivatization of products was investigated. Through 3 steps a novel 3,3’-disubsituted oxindole bearing adjacent quaternary-tertiary center was afforded. Keywords: tbutyl hydrazones; catalytic asymmetric synthesis; derivatization; 3- substituted-3- hydroxyoxindole II 目录 目录 目 录 摘 要 I HYPERLINK \l _bookmark0 Abstract II HYPERLINK \l _bookmark1 1 前言 1 HYPERLINK \l _bookmark2 1.1 手性的意义 1 HYPERLINK \l _bookmark3 1.2 手性催化的意义 2 HYPERLINK \l _bookmark4 1.3 Trost 经典配体在不对称催化反应中的应用 2 HYPERLINK \l _bookmark5 1.4 腙类化合物在不对称催化中的应用 5 HYPERLINK \l _bookmark6 1.4.1 N-单取代腙在不对称催化反应中的应用 7 HYPERLINK \l _bookmark7 1.5 3,3’-二取代氧化吲哚骨架的构建 10 HYPERLINK \l _bookmark8 1.5.1 引言 10 HYPERLINK \l _bookmark9 1.5.2 通过靛红的不对称直接加成反应构建 3-取代