钯催化炔卤构建碳卤键和环化反应的研究
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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和炔卤都能很好地完成反应。同样条件下，炔卤与环辛烯发生[2+2]环加成反应得到环丁烯卤化合物。研究表明，张力相对较小的环辛烯与炔卤反应时，可能经过两次的钯插入得到环丁烯卤化钯中间体，再经还原消除得到环丁烯卤产物。
第四章描述了一种简便直接合成(Z)-2-卤-1-氟烯的方法。该反应以末端炔为原料，NBS为溴源，氟化银为氟源。反应首先生成炔卤，进一步在氟化银的作用下高区域和立体选择性合成(Z)-2-卤-1-氟烯产物。该反应通过一锅法从末端炔直接合成目标产物。反应条件简单，官能团兼容性好，不使用腐蚀性原料。在反应中，氟化银既是合成炔卤的催化剂，同时又充当氟化反应的氟源。同时，非活化碳碳三键不会参与反应，但贫电子炔烃可以与氟化银反应得到氟化产物。
第五章论述在醋酸钯的催化和氟化铯的促进下，以炔卤、异腈为原料，一锅法合成5-氨基吡咯酮的反应。该反应可能首先通过氟化铯促进异腈与炔卤的亲核加成反应合成了卤代烯基酰胺，然后零价钯对卤代烯基酰胺的碳溴键氧化加成，接着异腈与烯基钯中间体的1,1-迁移插入，环化、还原消除得到5-氨基吡咯酮产物。
另外，在我们对炔卤的持续研究中，我们还发现了一种新颖的钯催化碳卤化反应，通过炔卤和炔卤之间的加成偶联反应可以顺利得到炔烯二卤产物，该方法具有良好的化学选择性，反应条件温和和收率高等优点。最后，我们还发现钯催化炔溴、烯烃、一氧化碳和甲醇的四组分反应可以顺利得到δ-炔基-γ-酯基化合物，该部分工作正在整理当中。
最后介绍了攻读博士学位期间的研究总结、所获得的研究成果状况、以及致谢等。
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 method forthe synthesis of bromo alkenynes. Furthermore, an unusual mechanism was proposed torationalize the observations.
In chapter3, The palladium-catalyzed intermolecular reaction of haloalkynes withnorbornene derivatives leads to7-alkynyl norbornane products. Forming a non-classical“norbornonium” cation or bridging palladium, which can rearrange the substituent at2-C to7-C, and then furnishing a7-C functionalization is key for the success of this reaction. In thesimilar condition, the [2+2] cycloaddition of haloalkynes with cyclooctene has been achieved in moderate to good yields.
In chapter4, Difunctionalization of terminal alkynes was achieved with AgF and NBS ashalogen sources. The presence of the halide moiety greatly enhances the reactivity of the vinylfluoride compounds and probably can be transformed into various products that are difficulteven impossible to obtain via direct fluorination. Meanwhile, the monofluoroalkenes werefacilely synthesized via a highly chemo-and regioselective fluorination of electron-deficientC-C triple bonds using AgF as fluorinating reagent in good yields.
In chapter5, we have developed a new strategy for the synthesis of bromoacrylamidesand polysubstituted iminopyrrolinones in good to excellent yields from readily availablestarting materials. This chemistry proceeds smoothly under the optimal reaction conditionsand various functional groups can be tolerated with exceptional selectivity. The methodologyis highly practical and it provides a straightforward approach to a series of5-iminopyrroloneand haloacrylamides in regioselective manner.
In addition, a new general carbohalogenation procedure to couple haloalkynes underpalladium catalysis is described. The bromoalkynylation reaction is chemoselective andallows preparation of a vast array of simple and high functionalized internal alkynes in highyields. The palladium-catalyzed haoloalkynes, cycloalkenes, carbon monoxide and methanolprovides an efficicent approach to interesting f δ-alkynyl-γ-ester compounds in good yields.The part of the work is coming soon.
Finally the research summary, research achievements, and acknowledgement areintroducted successively.
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和炔卤都能很好地完成反应。同样条件下，炔卤与环辛烯发生[2+2]环加成反应得到环丁烯卤化合物。研究表明，张力相对较小的环辛烯与炔卤反应时，可能经过两次的钯插入得到环丁烯卤化钯中间体，再经还原消除得到环丁烯卤产物。
第四章描述了一种简便直接合成(Z)-2-卤-1-氟烯的方法。该反应以末端炔为原料，NBS为溴源，氟化银为氟源。反应首先生成炔卤，进一步在氟化银的作用下高区域和立体选择性合成(Z)-2-卤-1-氟烯产物。该反应通过一锅法从末端炔直接合成目标产物。反应条件简单，官能团兼容性好，不使用腐蚀性原料。在反应中，氟化银既是合成炔卤的催化剂，同时又充当氟化反应的氟源。同时，非活化碳碳三键不会参与反应，但贫电子炔烃可以与氟化银反应得到氟化产物。
第五章论述在醋酸钯的催化和氟化铯的促进下，以炔卤、异腈为原料，一锅法合成5-氨基吡咯酮的反应。该反应可能首先通过氟化铯促进异腈与炔卤的亲核加成反应合成了卤代烯基酰胺，然后零价钯对卤代烯基酰胺的碳溴键氧化加成，接着异腈与烯基钯中间体的1,1-迁移插入，环化、还原消除得到5-氨基吡咯酮产物。
另外，在我们对炔卤的持续研究中，我们还发现了一种新颖的钯催化碳卤化反应，通过炔卤和炔卤之间的加成偶联反应可以顺利得到炔烯二卤产物，该方法具有良好的化学选择性，反应条件温和和收率高等优点。最后，我们还发现钯催化炔溴、烯烃、一氧化碳和甲醇的四组分反应可以顺利得到δ-炔基-γ-酯基化合物，该部分工作正在整理当中。
最后介绍了攻读博士学位期间的研究总结、所获得的研究成果状况、以及致谢等。
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 method forthe synthesis of bromo alkenynes. Furthermore, an unusual mechanism was proposed torationalize the observations.
In chapter3, The palladium-catalyzed intermolecular reaction of haloalkynes withnorbornene derivatives leads to7-alkynyl norbornane products. Forming a non-classical“norbornonium” cation or bridging palladium, which can rearrange the substituent at2-C to7-C, and then furnishing a7-C functionalization is key for the success of this reaction. In thesimilar condition, the [2+2] cycloaddition of haloalkynes with cyclooctene has been achieved in moderate to good yields.
In chapter4, Difunctionalization of terminal alkynes was achieved with AgF and NBS ashalogen sources. The presence of the halide moiety greatly enhances the reactivity of the vinylfluoride compounds and probably can be transformed into various products that are difficulteven impossible to obtain via direct fluorination. Meanwhile, the monofluoroalkenes werefacilely synthesized via a highly chemo-and regioselective fluorination of electron-deficientC-C triple bonds using AgF as fluorinating reagent in good yields.
In chapter5, we have developed a new strategy for the synthesis of bromoacrylamidesand polysubstituted iminopyrrolinones in good to excellent yields from readily availablestarting materials. This chemistry proceeds smoothly under the optimal reaction conditionsand various functional groups can be tolerated with exceptional selectivity. The methodologyis highly practical and it provides a straightforward approach to a series of5-iminopyrroloneand haloacrylamides in regioselective manner.
In addition, a new general carbohalogenation procedure to couple haloalkynes underpalladium catalysis is described. The bromoalkynylation reaction is chemoselective andallows preparation of a vast array of simple and high functionalized internal alkynes in highyields. The palladium-catalyzed haoloalkynes, cycloalkenes, carbon monoxide and methanolprovides an efficicent approach to interesting f δ-alkynyl-γ-ester compounds in good yields.The part of the work is coming soon.
Finally the research summary, research achievements, and acknowledgement areintroducted successively.
引文
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