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Transition Metal-Catalyzed Asymmetric Synthesis Based on Allene and Cyclopropane Chemistry

基于丙二烯和环丙烷化学的过渡金属催化不对称合成

基本信息

批准号：
13672228
负责人：
HIROI Kunio
金额：
$ 2.56万
依托单位：
Tohoku Pharmaceutical University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13672228/
关键词：
palladium catalyst allene asymmetric synthesis cyclopropane indole cycloaddition reaction 1, 3-dipolarophile cycloprpane

项目摘要

We have developed novel asymmetric synthetic methodologies with transition metal catalysts using allene and cyclopropane functionalities. Unsaturated compounds such as dienes and enynes are activated with metal catalysts to form new carbon-carbon bonds easily, providing carbocycles or heterocycles. Introduction of allene and cyclopropane functions in such systems provides much interest for us in term of their chemical characteristics for elaboration of complex organic molecules. Our recent results of the asymmetric reactions of allenes and cyclopropanes using metal catalysts are as follows.1. Asymmetric synthesis by asymmetric carbopalladation of allenes The palladium-catalyzed reaction of allenes with iodobenzene and nucleophiles using chiral phosphine ligands provided high enantioselectivity of α, β -functionalized compounds.2. Palladium-catalyzed reactions of allenes bearing iodophenyl groups with nucleophiles The palladium-catalyzed reactions of allenes bearing iodophenyl groups wi … More th nucleophiles provided directly tricyclic compounds by intramolecular carbopalladation followed by intramolecular nucleophilic substitution.3. Asymmetric synthesis of heterocycles by palladium-catalyzed reactions of allenes The palladium-catalyzed reactions of allenes bearing iodophenyl groups with nucleophiles were carried out in the presence of chiral phosphine ligands to give optically active tricyclic compounds with high enantioselectivity. On the use of amino components as nucleophiles, asymmetric synthesis of cyclic indole compounds was achieved with high enantioefficiency.4. Intramolecular metal-catalyzed reactions of allene-ene compounds Titanium-catalyzed reactions of allene-ene systems provided intramolecular cycloaddition products, [2+2] cycloaddition and ene reaction products. The stereospecificity of the reactions was obtained by appling the reactions to chiral allene systems.5. Palladium-catalyzed reactions of cyclopropylidenemethylcyclopropane systemsThe palladium-catalyzed reactions of cyclopropylidenemethylcyclopropane systems with electrophilic olefin provided [3+2] cycloaddition reaction products in high yields. This result indicates the existence of rather reactive 1, 3-dipolarophiles generated by the palladium-catalyzed reactions. Less

我们已经开发了新的不对称合成方法与过渡金属催化剂使用联烯和环丙烷功能。不饱和化合物如二烯和烯炔用金属催化剂活化以容易地形成新的碳-碳键，提供碳环或杂环。在这类体系中引入丙二烯和环丙烷官能团，使我们对它们的化学特性产生了很大的兴趣，从而为复杂有机分子的精细化提供了可能。我们最近在金属催化下联烯和环丙烷的不对称反应方面的研究结果如下：1.联烯的不对称碳钯化不对称合成联烯与碘苯及亲核试剂的手性膦配体钯催化反应提供了高的α，β -功能化化合物的对映选择性.钯催化的含碘苯基联烯与亲核试剂的反应 ...更多信息亲核试剂通过分子内碳钯化反应和分子内亲核取代反应直接生成三环化合物.钯催化联烯不对称合成杂环化合物在手性膦配体存在下，钯催化含碘苯基的联烯与亲核试剂反应，得到了高对映选择性的光学活性三环化合物。利用氨基组分作为亲核试剂，实现了环状吲哚类化合物的不对称合成，具有较高的对映效率.钛催化的联烯-烯体系的反应提供了分子内环加成产物、[2+2]环加成产物和烯反应产物。将反应应用于手性联烯体系，得到了反应的立体专一性.钯催化的亚环丙基甲基环丙烷体系的反应亚环丙基甲基环丙烷体系与亲电烯烃的反应以高产率提供[3+2]环加成反应产物。这一结果表明钯催化反应生成的反应活性较高的1，3-偶极亲电体的存在。少