铑催化的C-H键活化及钯催化的偶联反应的研究
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摘要
在当今有机合成化学中,C-C和C-O键的形成占有主导地位。而过渡金属催化构造C-C和C-O键是最为有用和强大的手段之—。本文将围绕这个主题展开研究。本论文共两个部分:1.铑催化的C-H键活化的研究。2.钯催化的偶联反应研究。
第一部分综述了近年来铑催化的C-H键活化的反应在有机化学反应中的应用,应研究和探讨铑催化的三类反应及应用:(1)发展了铑催化的C-H活化邻位芳基酰化反应体系,体系能兼容性好,反应不需要额外的氧化剂。(2)发展了铑催化芳基硼酸与邻苯二甲醛生成3-芳基-2-苯并呋喃酮反应体系,体系简单,操作方便,能兼容三氟甲基、硝基、氯、乙烯基等官能团。(3)发展了铑催化的二芳基乙炔自身聚合形成1,2,3-三芳基萘衍生物体系。
第二部分研究和探讨钯催化的两类偶联反应及应用:(1)发展了一种高效的钯催化的芳基三甲氧基硅烷与端炔偶联的反应体系。特别值得注意的是,吸电子的端炔也是良好的反应底物。可以视为对传统Sonogashira反应的一种重要补充。(2)发展了钯催化的芳基三甲氧基硅烷参与的Mizoroki-Heck类型反应体系,反应条件温和,产率良好。
The transition-metal-catalyzed reactions are simple, efficient and versatile routes to the formation of C-C and C-O bonds, which represents the key step in a wide range of preparative organic processes. This dissertation consisted of two parts. The first one is focused on rhodium-catalyzed C-H bond activation. The second is focused on the palladium-catalyzed cross-coupling reactions and their applications in organic synthesis.
In part one rhodium-catalyzed C-H bond activation in recent years were simply reviewed. Next, three reactions were studied as follows: (1) A rhodium-catalyzed ortho-benzoxylation of sp2 C-H bond by carboxylic acids was described. The procedure enjoys high efficiency, good functional group compatibility. Importantly, no external oxidant was required for the transformation. (2) A rhodium-catalyzed addition of aryl and alkenyl boronic acids to phthalaldehyde followed by an intramolecular aldehydic C-H bond esterification is described. It represents a facile and practical methodology to access 3-aryl and alkenyl phthalides in moderate to good yields. The procedure tolerates a series of functional groups, such as trifluoromethoxyl, nitro, methoxyl, fluoro, chloro and vinyl groups. (3) An efficient rhodium-catalyzed dimerization of diaryl acetylenes was achieved. Which provides the 1,2,3-triaryl naphthalene derivatives in moderate to good yields.
In part two two cross-coupling reactions catalyzed by palladium were studied as follows: (1) A palladium-catalyzed crosscoupling reaction of aryl trimethoxysiloxanes with terminal alkynes was described. It is notable that the electron-deficient terminal alkynes also worked well in the procedure, which represents a practical alternative for the Sonogashira reaction. (2) A palladium-catalyzed Mizoroki-Heck-type reaction of aryl trimethoxysilanes with olefin was successfully developed. A series of ArSi(OMe)3 and olefins, including electron-rich and deficient analogues worked well in the procedure, affording the arylation products in moderate to good yields.
第一部分综述了近年来铑催化的C-H键活化的反应在有机化学反应中的应用,应研究和探讨铑催化的三类反应及应用:(1)发展了铑催化的C-H活化邻位芳基酰化反应体系,体系能兼容性好,反应不需要额外的氧化剂。(2)发展了铑催化芳基硼酸与邻苯二甲醛生成3-芳基-2-苯并呋喃酮反应体系,体系简单,操作方便,能兼容三氟甲基、硝基、氯、乙烯基等官能团。(3)发展了铑催化的二芳基乙炔自身聚合形成1,2,3-三芳基萘衍生物体系。
第二部分研究和探讨钯催化的两类偶联反应及应用:(1)发展了一种高效的钯催化的芳基三甲氧基硅烷与端炔偶联的反应体系。特别值得注意的是,吸电子的端炔也是良好的反应底物。可以视为对传统Sonogashira反应的一种重要补充。(2)发展了钯催化的芳基三甲氧基硅烷参与的Mizoroki-Heck类型反应体系,反应条件温和,产率良好。
The transition-metal-catalyzed reactions are simple, efficient and versatile routes to the formation of C-C and C-O bonds, which represents the key step in a wide range of preparative organic processes. This dissertation consisted of two parts. The first one is focused on rhodium-catalyzed C-H bond activation. The second is focused on the palladium-catalyzed cross-coupling reactions and their applications in organic synthesis.
In part one rhodium-catalyzed C-H bond activation in recent years were simply reviewed. Next, three reactions were studied as follows: (1) A rhodium-catalyzed ortho-benzoxylation of sp2 C-H bond by carboxylic acids was described. The procedure enjoys high efficiency, good functional group compatibility. Importantly, no external oxidant was required for the transformation. (2) A rhodium-catalyzed addition of aryl and alkenyl boronic acids to phthalaldehyde followed by an intramolecular aldehydic C-H bond esterification is described. It represents a facile and practical methodology to access 3-aryl and alkenyl phthalides in moderate to good yields. The procedure tolerates a series of functional groups, such as trifluoromethoxyl, nitro, methoxyl, fluoro, chloro and vinyl groups. (3) An efficient rhodium-catalyzed dimerization of diaryl acetylenes was achieved. Which provides the 1,2,3-triaryl naphthalene derivatives in moderate to good yields.
In part two two cross-coupling reactions catalyzed by palladium were studied as follows: (1) A palladium-catalyzed crosscoupling reaction of aryl trimethoxysiloxanes with terminal alkynes was described. It is notable that the electron-deficient terminal alkynes also worked well in the procedure, which represents a practical alternative for the Sonogashira reaction. (2) A palladium-catalyzed Mizoroki-Heck-type reaction of aryl trimethoxysilanes with olefin was successfully developed. A series of ArSi(OMe)3 and olefins, including electron-rich and deficient analogues worked well in the procedure, affording the arylation products in moderate to good yields.
引文
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