过渡金属参与的不饱和键分子内环化反应及其选择性调控

项目名称： 过渡金属参与的不饱和键分子内环化反应及其选择性调控

项目编号： No.20872037

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 金属学与金属工艺

项目作者： 李艳忠

作者单位： 华东师范大学

项目金额： 30万元

中文摘要： 过渡金属参与的分子内环化反应是研究反应机理、构筑碳环、杂环化合物物的重要手段。本研究利用一系列官能团化的不饱和物的分子，研究其在过渡金属作用下的分子内环化反应和接续串联反应，发展了一些高收率、高选择性的碳-碳键、碳-杂原子键形成新反应、新方法。本研究主要开展了以下几方面的工作：（1）发展了钯/铜催化的合成3-醛基多取代呋喃衍生物的新方法，研究了其可能的反应机理。（2）发展了利用水杨醛，二级胺以及端炔为原料的多组分合成2，3 - 二取代苯并呋喃类化合物的新方法，该方法原料易得，避免了多步反应多次分离，简化了操作。（3）研究了FeCl3 催化的串联反应合成3-羰基喹啉类化合物的合成新方法。（4）铁催化的碳-氢键直接官能团化合成二苯并吡喃类衍生物。（5）研究了铁催化的端炔与烯基碘的偶联反应，选择性合成反式烯炔类化合物的新体系（6）发展了铁催化的选择性氧环化反应合成苯并吡喃类衍生物的新方法。（7）发展了Lewis酸催化合成1，4-二氢吡啶衍生物的新方法，这种方法有很好的官能团容忍性，收率良好。（8）发展了银催化的串联反应合成 2-取代喹啉类化合物的新体系，效果良好。

中文关键词： 过渡金属；分子内环化；杂环；催化；选择性

英文摘要： The intramolecular cyclization is one of the most straightforward way for the construction of carbocycles and/or heterocycles with regard to chemo-, regioselectivity. Our research work in this project focus on the development of novel synthetic protocols for the construction of new C-C and C-X bonds in an intramolecular manner. It includes the following parts: (a)Pd/Cu-Catalyzed Cascade Sonogashira coupling/Cyclization Reactions to Highly Substituted 3-Formyl Furans, in which an efficient palladium/copper-catalyzed approach to the synthesis of highly substituted 3-formyl furans from the reactions of readily available ?-bromoenaminones with terminal alkynes has been developed. (b)New Domino Approach for the Synthesis of 2,3-Disubstituted Benzo[b]furans via Copper-catalyzed Multi-component Coupling Reactions followed by Cyclization. (c) Iron-catalyzed Cascade Reaction of Ynone with o-Aminoaryl Compounds: A Michael Addition-cyclization Approach to 3-Carbonyl Quinolines (d)Iron-Catalyzed, Microwave-Promoted, One-Pot Synthesis of 9-Substituted Xanthenes by a Cascade Benzylation-Cyclization Process. An efficient Iron-catalyzed, microwave-promoted cascade benzylation-cyclization of phenols is reported. Benzyl acetates, benzyl bromides and benzyl carbonates are suitable benzylating reagents. The reactions proceed to afford both 9-aryl and 9-alkyl xanthene derivatives in good to high yields using FeCl3 as the catalyst under MW irradiation conditions.(e)Iron Catalyzed Cross-Coupling Reactions of Terminal Alkynes with Vinyl Iodides. The reaction was applicable to various acetylenes and vinyl iodides. The present reaction provides an efficient, environmentally friendly protocol to conjugated enyne derivatives in good to excellent yields under mild conditions.(f)Iron-catalyzed Regioselective Hydroaryloxylation of C-C Triple Bonds: An Efficient Synthesis of 2H-1-Benzopyran Derivatives (g)Acid-Catalyzed Cascade Reactions of Enaminones with Aldehydes: A C-H Functionalization Approach to 1,4-Dihydropyridines (h)Silver-catalyzed Cascade Reaction of o-Aminoaryl Compounds with Alkynes: An Aniline Mediated Synthesis of 2-Substituted Quinolines.

英文关键词： transition metals; intramolecular cycliztion; heterocycle; catalysis; selectivity