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Ni催化炔烃和环氧化物还原偶合反应的密度泛函研究 被引量:1
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作者 吕文阳 李明 孟庆喜 《西南师范大学学报(自然科学版)》 CAS CSCD 北大核心 2006年第1期95-103,共9页
用密度泛函方法(DFT)研究Ni催化炔烃和环氧化物还原偶合反应.在B3LYP/6-31G(d,P)计算水平上优化了所有结构.结果表明,反应是放热的.具有四元环和六元环中间体,β—H(10)的还原消去反应是整个反应的速率决定步骤.理论预测的主要产物是与... 用密度泛函方法(DFT)研究Ni催化炔烃和环氧化物还原偶合反应.在B3LYP/6-31G(d,P)计算水平上优化了所有结构.结果表明,反应是放热的.具有四元环和六元环中间体,β—H(10)的还原消去反应是整个反应的速率决定步骤.理论预测的主要产物是与实验吻合的(2R)-4-已烯-2-醇. 展开更多
关键词 炔烃和环氧化物的还原偶合 NI催化剂 反应机理
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在碱金属/液氨作用下两类还原反应的机理探讨 被引量:1
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作者 戴亚中 裴坚 《大学化学》 CAS 2015年第4期58-62,共5页
碱金属/液氨溶液具有很强还原性,在有机合成中有着广泛的运用。在高等教育出版社出版的由邢其毅、裴伟伟、徐瑞秋以及裴坚等人编著的《基础有机化学》(第3版)中描述了在碱金属/液氨作用条件下的两类还原反应:炔烃被还原为烯烃的反应和Bi... 碱金属/液氨溶液具有很强还原性,在有机合成中有着广泛的运用。在高等教育出版社出版的由邢其毅、裴伟伟、徐瑞秋以及裴坚等人编著的《基础有机化学》(第3版)中描述了在碱金属/液氨作用条件下的两类还原反应:炔烃被还原为烯烃的反应和Birch还原反应。一般认为这两种反应均生成了自由基负离子中间体。本文结合近几年的文献报道,对它们的机理进行进一步的探讨。 展开更多
关键词 有机化学 炔烃还原 Birch还原 反应机理 探讨
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Visible light promoted difunctionalization reactions of alkynes 被引量:4
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作者 Xiang Ren Zhan Lu 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2019年第7期1003-1019,共17页
Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, an... Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved. 展开更多
关键词 Visible light photocatalysis Difunctionalization CYCLIZATION ALKYNE Redox catalyst
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Photoredox-catalyzed [4+2] annulation of cyclobutylanilines with alkenes, alkynes, and diynes in continuous flow
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作者 Jiang Wang Theresa H.Nguyen Nan Zheng 《Science China Chemistry》 SCIE EI CAS CSCD 2016年第2期180-183,共4页
Continuous flow has recently emerged as a powerful enabling technology that greatly improves many reactions' efficiency. Here, we apply the technology to intermolecular [4+2] annulation of cyclobutylanilines with ... Continuous flow has recently emerged as a powerful enabling technology that greatly improves many reactions' efficiency. Here, we apply the technology to intermolecular [4+2] annulation of cyclobutylanilines with alkenes, alkynes, and diynes by photoredox catalysis. An across-the-board improvement in the annulation's efficiency is noticed. Moreover, a gram-scale annulation is successfully demonstrated in continuous flow using a much lower catalyst loading. 展开更多
关键词 PHOTOCATALYSIS continuous flow N-cyclobutylanfline [4+2] ANNULATION visible light
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