氟烷基亚胺酰卤衍生物合成含氟杂环化合物的反应研究
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摘要
含氟的各类杂环化合物,由于其往往相对于不含氟类似物,具有更为特殊的生理活性性质,越来越受到研究人员的关注。可以说,现在开发任何一种新药物,都必须对其含氟类似物进行活性测试和筛选,因此,就需要合成各种各样的基于天然化合物的或者基于全新结构的含氟化合物,以用来进行生物活性评估。然而许多情况下,合成一般有机化合物的方法,往往不适用于含氟底物,而且往往只有在分子的特定位置引入含氟基团才能起到改善其生理活性的作用,所以,开展多样的有效的方法学来合成我们所需的含氟目标分子就显得十分必要。
本论文主要研究了氟烷基胺基烯酮和氟烷基炔基亚胺两个含氟砌块的反应,通过过渡金属的参与,合成了一系列有潜在价值的含氟杂环分子。主要分为以下五部分:
1)研究了氟烷基胺基烯酮的分子内亲卤反应,以较好的产率合成2,2-二氟-2,3-二氢呋喃,同时研究了分子间串联反应的可能性,得到了多取代的二氢呋喃化合物;在底物的扩展过程中,还意外得到了3,3-二氟-2,3-二氢吲哚化合物;同时我们也对二氢呋喃化合物进行了衍生化。
2)研究了氟烷基胺基烯酮与末端芳基炔烃在钯催化下的Sonogashira/分子内亲核加成串联反应,以优秀的产率合成了一系列的2-三氟甲基喹啉化合物。同时将方法学应用到不含氟的分子中,也取得了不错的结果。
3)研究了氟烷基-N-(邻卤芳基)炔基亚胺的分子内碳钯化反应合成了2-三氟甲基吲哚产物;同时通过改变反应思路,使用氟烷基炔基亚胺和芳基碘代物通过一个钯催化的基于碳氢键活化的分子间串联反应,合成了一系列3H-吲哚化合物,并对其还原反应进行了拓展;该方法学同样也能用于不含氟的底物。
4)研究了氟烷基-N-(邻卤芳基)炔基亚胺与叠氮化钠在碘化亚铜催化下的串联反应,合成一类结构新颖的4-氟烷基-[1,2,3]三唑[1,5-a]喹喔啉化合物。
5)研究了氟烷基炔基亚胺与苄胺的串联反应,通过碳氟键断裂合成了一系列3-氟(氟烷基)吡啶化合物;同时通过对碱的控制,选择性的合成了另一类氟烷基二氢嘧啶化合物,为这两类杂环的合成提供了一种全新的路线。
Fluorinated heterocycles have received considerable attention in recent years due to their unique chemical and biological properties compared with non-fluorinated analogs. It would not be an exaggeration to say that currently every new drug discovery and development program without exception explores fluorine-containing drug candidates. Therefore, a wide variety of fluorine-containing compounds based either on known natural products or on new skeletons is needed for biological evaluation. However, in many cases, synthetic methods developed for ordinary organic molecules do not work well for fluorochemicals because of their unique reactivity, and selective introduction of fluorine into molecule at a specified position is another challenge. So it is necessary to develop efficient synthetic methods applicable to fluorine-containing organic compounds.
This dissertation is focused on the study of reactions of fluoroalkyl enaminoketones and fluoroalkyl alkynylimines, and its application in fluoro-heterocycle synthesis through transition metal catalysis. It consists of five chapters.
1)An efficient strategy for the synthesis of 2,2-difluoro-2,3-dihydrofuran products fromβ-fluoroalkyl-β-enaminoketones is described. The reaction occurred via intramolecular halophilic attack-initiated cascade process. A series of 2,3-dihydrofurans were prepared in high yields. And an intermolecular domino process achieved providing polysubstituted dihydrofurans.
2 ) A new, rapid and high-yielding method to prepare 3,4-disubstituded 2-trifluoromethylquinolines by palladium catalyzed tandem Sonogashira?alkyne carbocyclization ofβ-trifluoromethylβ-enaminoketones with aryl alkynes is described. This reaction can also be expanded to the non-fluorine containing substrates.
3)Treatment of various types of N-(o-haloaryl)alkynylimines in the presence of palladium catalyst gave 2-trifluoromethyl indoles in high yields. Another strategy developed through Pd-catalyzed cascade carbopalladation/C-H activation process using fluoroalkyl alkynylimines and aryl iodides provided a series of 2-fluoroalkyl 3-methylene-3H-indoles in good yields. Method for reduction of these products was also developed. This reaction can also be expanded to the non-fluorine containing substrates.
4)Novel tricyclic 4-(trifluoromethyl)-[1,2,3]triazolo[1,5-a]quinoxalines were readily prepared from N-(o-haloaryl)alkynylimines and sodium azide via copper(I)-catalyzed tandem reactions.
5)A chemoselective strategy for the synthesis of poly-substituted pyridines and fluoroalkyl dihydropyrimidines based on C-F bond breaking of the anionically activated fluoroalkyl group was described. A series of pyridines and dihydropyrimidines were prepared through this domino process in high yields under noble metal-free conditions.
本论文主要研究了氟烷基胺基烯酮和氟烷基炔基亚胺两个含氟砌块的反应,通过过渡金属的参与,合成了一系列有潜在价值的含氟杂环分子。主要分为以下五部分:
1)研究了氟烷基胺基烯酮的分子内亲卤反应,以较好的产率合成2,2-二氟-2,3-二氢呋喃,同时研究了分子间串联反应的可能性,得到了多取代的二氢呋喃化合物;在底物的扩展过程中,还意外得到了3,3-二氟-2,3-二氢吲哚化合物;同时我们也对二氢呋喃化合物进行了衍生化。
2)研究了氟烷基胺基烯酮与末端芳基炔烃在钯催化下的Sonogashira/分子内亲核加成串联反应,以优秀的产率合成了一系列的2-三氟甲基喹啉化合物。同时将方法学应用到不含氟的分子中,也取得了不错的结果。
3)研究了氟烷基-N-(邻卤芳基)炔基亚胺的分子内碳钯化反应合成了2-三氟甲基吲哚产物;同时通过改变反应思路,使用氟烷基炔基亚胺和芳基碘代物通过一个钯催化的基于碳氢键活化的分子间串联反应,合成了一系列3H-吲哚化合物,并对其还原反应进行了拓展;该方法学同样也能用于不含氟的底物。
4)研究了氟烷基-N-(邻卤芳基)炔基亚胺与叠氮化钠在碘化亚铜催化下的串联反应,合成一类结构新颖的4-氟烷基-[1,2,3]三唑[1,5-a]喹喔啉化合物。
5)研究了氟烷基炔基亚胺与苄胺的串联反应,通过碳氟键断裂合成了一系列3-氟(氟烷基)吡啶化合物;同时通过对碱的控制,选择性的合成了另一类氟烷基二氢嘧啶化合物,为这两类杂环的合成提供了一种全新的路线。
Fluorinated heterocycles have received considerable attention in recent years due to their unique chemical and biological properties compared with non-fluorinated analogs. It would not be an exaggeration to say that currently every new drug discovery and development program without exception explores fluorine-containing drug candidates. Therefore, a wide variety of fluorine-containing compounds based either on known natural products or on new skeletons is needed for biological evaluation. However, in many cases, synthetic methods developed for ordinary organic molecules do not work well for fluorochemicals because of their unique reactivity, and selective introduction of fluorine into molecule at a specified position is another challenge. So it is necessary to develop efficient synthetic methods applicable to fluorine-containing organic compounds.
This dissertation is focused on the study of reactions of fluoroalkyl enaminoketones and fluoroalkyl alkynylimines, and its application in fluoro-heterocycle synthesis through transition metal catalysis. It consists of five chapters.
1)An efficient strategy for the synthesis of 2,2-difluoro-2,3-dihydrofuran products fromβ-fluoroalkyl-β-enaminoketones is described. The reaction occurred via intramolecular halophilic attack-initiated cascade process. A series of 2,3-dihydrofurans were prepared in high yields. And an intermolecular domino process achieved providing polysubstituted dihydrofurans.
2 ) A new, rapid and high-yielding method to prepare 3,4-disubstituded 2-trifluoromethylquinolines by palladium catalyzed tandem Sonogashira?alkyne carbocyclization ofβ-trifluoromethylβ-enaminoketones with aryl alkynes is described. This reaction can also be expanded to the non-fluorine containing substrates.
3)Treatment of various types of N-(o-haloaryl)alkynylimines in the presence of palladium catalyst gave 2-trifluoromethyl indoles in high yields. Another strategy developed through Pd-catalyzed cascade carbopalladation/C-H activation process using fluoroalkyl alkynylimines and aryl iodides provided a series of 2-fluoroalkyl 3-methylene-3H-indoles in good yields. Method for reduction of these products was also developed. This reaction can also be expanded to the non-fluorine containing substrates.
4)Novel tricyclic 4-(trifluoromethyl)-[1,2,3]triazolo[1,5-a]quinoxalines were readily prepared from N-(o-haloaryl)alkynylimines and sodium azide via copper(I)-catalyzed tandem reactions.
5)A chemoselective strategy for the synthesis of poly-substituted pyridines and fluoroalkyl dihydropyrimidines based on C-F bond breaking of the anionically activated fluoroalkyl group was described. A series of pyridines and dihydropyrimidines were prepared through this domino process in high yields under noble metal-free conditions.
引文
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