过渡金属催化的C-H官能化及C-B键氧化反应研究
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摘要
过渡金属催化的C-H官能化已经成为有机化学研究的一个热点,其中,钯和铑催化的C-H官能化已经有了大量的研究,并在合成复杂芳香性碳环和杂环方面显示了巨大的潜力。本论文主要研究了金属钌复合物催化的包含有C-H官能化步骤的串联反应,并研究了其合成应用。
首先,我们发展了单一钌卡宾催化剂催化的烯烃交叉复分解/分子内氢芳香化串联环化反应,实现了吲哚C-3位sp2C-H官能化,高效构建了结构多样的C-4位取代的四氢咔唑衍生物(收率高达98%)。此外,考虑到多环吲哚骨架中N-1位上的取代基对其本身的生物活性以及药理活性的重要影响,我们将N-苯基保护的吲哚基烯烃应用到这一策略中,合成了一系列的N-苯基保护的四氢咔唑化合物(收率：81-88%)。
其次,我们利用光氧化还原催化剂与过渡金属协同催化的策略,实现了三级胺氮原子的a-sp3C-H键的氧化-不对称炔基化串联反应,立体选择性地构建了一系列多取代的四氢异喹啉衍生物。这类化合物经过简单的合成转化就可以得到具有重要生物活性化合物的重要合成中间体。这一工作为可见光催化的不对称合成提供了一个新的思路。
最后,我们利用可见光催化的空气参与的烯基硼酸的C-B键氧化断裂,成功实现了多取代醛、酮等羰基化合物的制备。该反应适用于芳基烯基硼酸、烷基烯基硼酸、直链的烯基硼酸以及环状的烯基硼酸,为羰基化合物的合成提供了一条新的途径。此外,有机染料也可以成功催化这一C-B键氧化反应,可以高收率的得到相应的羰基化合物(收率高达86%)。
Transition metals catalysis is one of the most important strategies in current organic chemistry. In particular, transition metal-catalyzed C-H functionalization provides an elegant method for the rapid construction of complex molecules. This dissertation is mainly focused on the studies of ruthenium catalyzed cascade reaction involving C-H functionalizations.
1. We have developed a single ruthenium-catalyzed cross-metathesis/intramolecular-hydroarylation cascade, which offeres a practical and efficient synthesis of structurally diverse and complex tetrahydrocarbazoles in good to excellent yields (up to98%) via a sp2C-H functionalization at C-3position of indole. It was documented that the substituents on the N-1position of polycyclic indoles had great effects on their biological activities. As a result, N-phenyl indolyl alkene was applied to this strategy, which could provide various N-phenyl substituted tetrahydrocarbazoles in good yields (81-88%).
2. An asymmetric functionalization of sp3C-H bonds adjacent to a nitrogen atom in tetrahydroisoquinolines, by the combination of the photocatalytic aerobic oxidation and the metal-catalyzed alkynylation reaction, have been described. Biologically important chiral tetrahydroisoquinoline alkaloids could be obtained by the use of this novel dual catalysis procedure.
3. An efficient approach to carbonyl compounds has been disclosed through an aerobic oxidative cleavage of C-B bond using visible-light photoredox. This procedure has a wide broad substrates scopes and high functional group tolerance. More importantly, some organic dyes can be employed as photocatalysts in the oxidative cleavage reaction under irradiation by visible light, affording the corresponding carbonyl compounds in high yields (up to86%).
首先,我们发展了单一钌卡宾催化剂催化的烯烃交叉复分解/分子内氢芳香化串联环化反应,实现了吲哚C-3位sp2C-H官能化,高效构建了结构多样的C-4位取代的四氢咔唑衍生物(收率高达98%)。此外,考虑到多环吲哚骨架中N-1位上的取代基对其本身的生物活性以及药理活性的重要影响,我们将N-苯基保护的吲哚基烯烃应用到这一策略中,合成了一系列的N-苯基保护的四氢咔唑化合物(收率：81-88%)。
其次,我们利用光氧化还原催化剂与过渡金属协同催化的策略,实现了三级胺氮原子的a-sp3C-H键的氧化-不对称炔基化串联反应,立体选择性地构建了一系列多取代的四氢异喹啉衍生物。这类化合物经过简单的合成转化就可以得到具有重要生物活性化合物的重要合成中间体。这一工作为可见光催化的不对称合成提供了一个新的思路。
最后,我们利用可见光催化的空气参与的烯基硼酸的C-B键氧化断裂,成功实现了多取代醛、酮等羰基化合物的制备。该反应适用于芳基烯基硼酸、烷基烯基硼酸、直链的烯基硼酸以及环状的烯基硼酸,为羰基化合物的合成提供了一条新的途径。此外,有机染料也可以成功催化这一C-B键氧化反应,可以高收率的得到相应的羰基化合物(收率高达86%)。
Transition metals catalysis is one of the most important strategies in current organic chemistry. In particular, transition metal-catalyzed C-H functionalization provides an elegant method for the rapid construction of complex molecules. This dissertation is mainly focused on the studies of ruthenium catalyzed cascade reaction involving C-H functionalizations.
1. We have developed a single ruthenium-catalyzed cross-metathesis/intramolecular-hydroarylation cascade, which offeres a practical and efficient synthesis of structurally diverse and complex tetrahydrocarbazoles in good to excellent yields (up to98%) via a sp2C-H functionalization at C-3position of indole. It was documented that the substituents on the N-1position of polycyclic indoles had great effects on their biological activities. As a result, N-phenyl indolyl alkene was applied to this strategy, which could provide various N-phenyl substituted tetrahydrocarbazoles in good yields (81-88%).
2. An asymmetric functionalization of sp3C-H bonds adjacent to a nitrogen atom in tetrahydroisoquinolines, by the combination of the photocatalytic aerobic oxidation and the metal-catalyzed alkynylation reaction, have been described. Biologically important chiral tetrahydroisoquinoline alkaloids could be obtained by the use of this novel dual catalysis procedure.
3. An efficient approach to carbonyl compounds has been disclosed through an aerobic oxidative cleavage of C-B bond using visible-light photoredox. This procedure has a wide broad substrates scopes and high functional group tolerance. More importantly, some organic dyes can be employed as photocatalysts in the oxidative cleavage reaction under irradiation by visible light, affording the corresponding carbonyl compounds in high yields (up to86%).
引文
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