导　　师： 江焕峰

学科专业： 081704

授予学位： 博士

作　　者： ;

机构地区： 华南理工大学

摘　　要： 发展简便直接的方法从廉价易得的原料合成复杂多官能团的有机分子是现代有机合成化学的研究热点之一。在有机合成化学中，炔卤是一种非常有研究意义、实用价值的有机合成砌块。与卤代烯烃的C/(sp2/)-X /(X=I, Br, Cl/)键相比，炔卤的C/(sp/)-X键具有更高的活性，反应后可产生碳碳三键官能团；与末端炔烯烃相比，炔卤的卤原子既作为活化基团，又起到定位基团作用。近年来，基于炔卤的官能团化反应受到广泛关注。例如：卤原子作为离去基团与炔烯烃、胺等发生偶联反应；基于卤原子定位效应的亲核加成反应；卤原子作为活化基团发生环化反应等。 我们的目标是以炔卤为基本原料，发展过渡金属催化选择性构建C/(sp/)-C/(sp~2/)、C-N、和C-X键等的方法，进而合成多官能团化的目标分子，如炔烯卤、环丁烯卤、含氟烯烃、含氮杂环等一系列新颖的化合物。这些研究结果将分五部份逐一介绍。 第一章为序论，首先简单阐述了各种炔卤化合物的制备方法，以及综述炔卤为原料选择性构建碳-碳、碳-氮、碳-氧键等策略，并利用这些策略合成一系列炔烃、烯炔、炔胺、炔醇和环化产物等。最后，介绍了本研究课题的研究目的、内容以及研究意义。 第二章论述了钯催化炔卤与内炔高区域和立体选择性的炔溴化反应，制备cis-炔烯溴化合物。该反应底物适用性范围广，条件温和，产率高。溴炔化产物可以进一步发生官能团修饰反应。该反应首先通过炔卤对零价钯的氧化加成反应得到炔钯中间体，再与内炔顺式插入，最后经碳钯卤键还原消除得到炔烯溴产物。 第三章介绍了在钯的催化下，炔卤对降冰片烯烃发生炔溴化反应，再经“桥钯化”迁移反应制备2-卤-7-炔基降冰片烷化合物。该反应底物适用范围广，带各种取代基的降冰片烯烃� The development of general and efficient methodologies for the synthesis of complexmolecular skeletons is the central focus of mordern organic chemistry. Haloalkynes areattractive starting materials in palladium-catalzyed transformations because they are highlyreactive and readily available from the inexpensive acetylides. Plus, they can tolerate variousreaction conditions and generally do not require additional oxidant or base. Halogen atomcould activate the triple bond and as the leaving group, the triple bond occurs thecross-coupling reaction with alkynes, akenes and amines etc; The halogen atom as thedirecting group which proceeds the nucleophilic addition reaction. The halogen atom as theactivating group which proceeds the annulation addition. In this context, we describe herein our recent explorations in the field of haloalkynechemistry. An array of broadly useful coupling methodologies has been developed for theformation of C/(sp/)-C/(sp~2/)、C-N and C-Br bonds etc. We further describe the application ofthese methods to the syntheses of complex systems, including the haloalkenyne, cyclobutylbromide, Bromofluoroalkenes, and heterocycles. Our research on activation andfunctionalization of alkynes has led to a series of new results which will be presented in thefollowing five chapters. In chapter1, we have introduced the reaction features of haloalkynes, the effectivesynthesis methods and the progress on selective C-C, C-N and C-X /(X=I, Br, Cl/) bondformation from haloalkynes and functionalization of haloalkynes has led to a series of alkynes,alkenes, Ynamides and cycloaddition products etc. Finally, introduces the significane of thisresearch subject. In chapter2, we have discovered a novel type of palladium-catalyzed cross-couplingreaction between bromoalkynes and internal alkynes. Direct cis-addition of bromoalkynes tovarious alkynes were found to take place to give difunctionalized enynes as products withPd/(II/) as a catalyst. The reaction condition was extremely easy, providing a facile met

关 键 词： 钯 有机合成 炔卤 炔烯溴 环丁烯卤 烯基氟 氨基吡咯酮

领　　域： [理学] [理学]