Suzuki-Miyaura reactions, involving the activation of carbon-halogen bonds, especially C-C1 bonds, have drawn widespread attention because of their huge industrial potential. However, these reactions are dependent on ...Suzuki-Miyaura reactions, involving the activation of carbon-halogen bonds, especially C-C1 bonds, have drawn widespread attention because of their huge industrial potential. However, these reactions are dependent on the development of highly active and stable catalysts. Herein, we developed a convenient one-pot wet route to synthesize PdxCuy bimetallic nanocrystals for the Suzuki-Miyaura reaction. By introducing Cu, an earth-abundant element, the catalytic activity was greatly enhanced while the amount of Pd required was reduced. PdxCuy nanocrystals of different compositions, including PdBCu, Pd2Cu, PdCu, PdCu2, and PdCu3, were successfully synthesized by tuning the Pd：Cu ratio. Their catalytic performance in Suzuki-Miyaura reactions between phenylboronic acid and halobenzenes （iodo-, bromo-, or chlorobenzene） showed that PdCua nanocatalyst demonstrated the best efficacy.展开更多
Polymer-supported phosphine ligand 3b derived from ferrocene was prepared, and applied in palladium-catalyzed Suzuki- Miyaura reactions. A range of aryl bromides can couple with phenylboronic acid to obtain correspond...Polymer-supported phosphine ligand 3b derived from ferrocene was prepared, and applied in palladium-catalyzed Suzuki- Miyaura reactions. A range of aryl bromides can couple with phenylboronic acid to obtain corresponding biaryls in excellent yields. The recycling of the polymer-bound catalyst was tested without adding palladium.展开更多
A simple and highly efficient protocol has been developed for the Pd/C-catalyzed ligand-free Suzuki- Miyaura reaction of potassium aryltrifluoroborates. In this catalytic system, the results demonstrate that oxygen pl...A simple and highly efficient protocol has been developed for the Pd/C-catalyzed ligand-free Suzuki- Miyaura reaction of potassium aryltrifluoroborates. In this catalytic system, the results demonstrate that oxygen plays a positive role in the cross-coupling reaction. In addition, this catalytic system could be successfully applied to synthesize biaryl compounds containing a carbazole moiety and the catalyst was recycled seven times without significant loss of catalytic activitv.展开更多
A simple and efficient catalytic system for Na2PdC14 catalyzing the Suzuki-Miyaura reaction of dibromoben- zene and arylboronic acid has been developed by using 2N2O-salen as a ligand in H2O/EtOH （V ： V=4 ： 1） at ...A simple and efficient catalytic system for Na2PdC14 catalyzing the Suzuki-Miyaura reaction of dibromoben- zene and arylboronic acid has been developed by using 2N2O-salen as a ligand in H2O/EtOH （V ： V=4 ： 1） at 100 ℃. Using this method, the reactions of substrates containing sterically demanding ortho substituents （e.g. dibromo- benzene and/or arylboronic acids） proceeded efficiently, with the corresponding terphenyl derivatives being pro- duced in moderate to excellent yields. Furthermore, this method offers interesting features for the multi-gram scale synthesis of terphenyl compound.展开更多
The Suzuki-Miyaura reaction of methyl-5-bromo-8-（tosyloxy）-1,6-naphthyridine-7-carboxylate（5）,with 2 equiv. of arylboronic acids gave diarylated product, 5,8–diaryl-1,6-naphthyridine-7-carboxylate（7）, whereas 1...The Suzuki-Miyaura reaction of methyl-5-bromo-8-（tosyloxy）-1,6-naphthyridine-7-carboxylate（5）,with 2 equiv. of arylboronic acids gave diarylated product, 5,8–diaryl-1,6-naphthyridine-7-carboxylate（7）, whereas 1 equiv. of arylboronic acid resulted in site-selective formation of 5-aryl-8-（tosyloxy）-1,6-naphthyridine-7-carboxylate（8）. The reactions proceeded with excellent chemo-selectivity in favor of the bromide group. Likewise, one-pot reaction with completely different boronic acids by sequential addition produced 1,6-naphthyridine-7-carboxylates,（10） containing two different aryl groups at 5 and 8 positions.展开更多
大力发展非磷配体的钯催化C-C偶联具有重要的理论意义和应用价值。本文设计合成了3个结构稳定、毒性小的卟啉钯配合物,并利用1 H NMR和IR对其结构进行了表征。3个配合物的催化活性结果表明:四(甲氧基苯基)卟啉钯(配合物3,0.1%mol催化剂...大力发展非磷配体的钯催化C-C偶联具有重要的理论意义和应用价值。本文设计合成了3个结构稳定、毒性小的卟啉钯配合物,并利用1 H NMR和IR对其结构进行了表征。3个配合物的催化活性结果表明:四(甲氧基苯基)卟啉钯(配合物3,0.1%mol催化剂量)能够在甲苯中有效地催化溴代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应,产率在32%～99%之间,TON值可达到6×104,同时反应过程中没有钯黑析出。展开更多
Suzuki-Miyaura金属偶联反应是在零价钯配合物的催化下,芳基硼酸或硼酸酯与卤代芳烃发生交叉偶联的过程。该反应具有很强的底物适应性和官能团容忍性,广泛应用于众多天然产物与有机材料的合成。鉴于反应的重要性,近年来国外高校逐渐尝试...Suzuki-Miyaura金属偶联反应是在零价钯配合物的催化下,芳基硼酸或硼酸酯与卤代芳烃发生交叉偶联的过程。该反应具有很强的底物适应性和官能团容忍性,广泛应用于众多天然产物与有机材料的合成。鉴于反应的重要性,近年来国外高校逐渐尝试将Suzuki-Miyaura反应引入到本科生的有机实验教学中。本文针对2000年后Journal of Chemical Education期刊中涉及的Suzuki-Miyaura反应,分别从反应条件、后处理和表征方法、实验拓展等多个方面进行了比较和归纳,并对其设计理念和教学特色进行了综述。展开更多
基金This research was supported in part by the National Natural Science Foundation of China （Nos. 21475007, 21275015 and 21505003）, and the Fundamental Research Funds for the Central Universities （Nos. YS1406, buctrc201507 and buctrc201608）. We also thank the support from the Innovation and Promotion Project of Beijing University of Chemical Technology, the Public Hatching Platform for Recruited Talents of Beijing University of Chemical Technology, the High- Level Faculty Program of Beijing University of Chemical Technology （No. buctrc201325）, and BUCT Fund for Disciplines Construction and Development （No. XK1526）.
文摘Suzuki-Miyaura reactions, involving the activation of carbon-halogen bonds, especially C-C1 bonds, have drawn widespread attention because of their huge industrial potential. However, these reactions are dependent on the development of highly active and stable catalysts. Herein, we developed a convenient one-pot wet route to synthesize PdxCuy bimetallic nanocrystals for the Suzuki-Miyaura reaction. By introducing Cu, an earth-abundant element, the catalytic activity was greatly enhanced while the amount of Pd required was reduced. PdxCuy nanocrystals of different compositions, including PdBCu, Pd2Cu, PdCu, PdCu2, and PdCu3, were successfully synthesized by tuning the Pd：Cu ratio. Their catalytic performance in Suzuki-Miyaura reactions between phenylboronic acid and halobenzenes （iodo-, bromo-, or chlorobenzene） showed that PdCua nanocatalyst demonstrated the best efficacy.
基金This work was financially supported by the Knowledge Innovation Program of the Chinese Academy of Sciences(DICP R200309)the National Basic Research Program of China(2003CB61615803)the National Natural Science Foundation of China(No.20473089).
文摘Polymer-supported phosphine ligand 3b derived from ferrocene was prepared, and applied in palladium-catalyzed Suzuki- Miyaura reactions. A range of aryl bromides can couple with phenylboronic acid to obtain corresponding biaryls in excellent yields. The recycling of the polymer-bound catalyst was tested without adding palladium.
基金financial support from the Nationa Natural Science Foundation of China (Nos. 21276043, 21421005)the Research Foundation of Dalian University of Technology for Retired Professors (No. DUTTX2015102)
文摘A simple and highly efficient protocol has been developed for the Pd/C-catalyzed ligand-free Suzuki- Miyaura reaction of potassium aryltrifluoroborates. In this catalytic system, the results demonstrate that oxygen plays a positive role in the cross-coupling reaction. In addition, this catalytic system could be successfully applied to synthesize biaryl compounds containing a carbazole moiety and the catalyst was recycled seven times without significant loss of catalytic activitv.
文摘A simple and efficient catalytic system for Na2PdC14 catalyzing the Suzuki-Miyaura reaction of dibromoben- zene and arylboronic acid has been developed by using 2N2O-salen as a ligand in H2O/EtOH （V ： V=4 ： 1） at 100 ℃. Using this method, the reactions of substrates containing sterically demanding ortho substituents （e.g. dibromo- benzene and/or arylboronic acids） proceeded efficiently, with the corresponding terphenyl derivatives being pro- duced in moderate to excellent yields. Furthermore, this method offers interesting features for the multi-gram scale synthesis of terphenyl compound.
基金the VIT University Vellore for the support and facilitiesSIF-VIT for their support of NMR(DST-FIST Fund)
文摘The Suzuki-Miyaura reaction of methyl-5-bromo-8-（tosyloxy）-1,6-naphthyridine-7-carboxylate（5）,with 2 equiv. of arylboronic acids gave diarylated product, 5,8–diaryl-1,6-naphthyridine-7-carboxylate（7）, whereas 1 equiv. of arylboronic acid resulted in site-selective formation of 5-aryl-8-（tosyloxy）-1,6-naphthyridine-7-carboxylate（8）. The reactions proceeded with excellent chemo-selectivity in favor of the bromide group. Likewise, one-pot reaction with completely different boronic acids by sequential addition produced 1,6-naphthyridine-7-carboxylates,（10） containing two different aryl groups at 5 and 8 positions.
文摘大力发展非磷配体的钯催化C-C偶联具有重要的理论意义和应用价值。本文设计合成了3个结构稳定、毒性小的卟啉钯配合物,并利用1 H NMR和IR对其结构进行了表征。3个配合物的催化活性结果表明:四(甲氧基苯基)卟啉钯(配合物3,0.1%mol催化剂量)能够在甲苯中有效地催化溴代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应,产率在32%～99%之间,TON值可达到6×104,同时反应过程中没有钯黑析出。
文摘Suzuki-Miyaura金属偶联反应是在零价钯配合物的催化下,芳基硼酸或硼酸酯与卤代芳烃发生交叉偶联的过程。该反应具有很强的底物适应性和官能团容忍性,广泛应用于众多天然产物与有机材料的合成。鉴于反应的重要性,近年来国外高校逐渐尝试将Suzuki-Miyaura反应引入到本科生的有机实验教学中。本文针对2000年后Journal of Chemical Education期刊中涉及的Suzuki-Miyaura反应,分别从反应条件、后处理和表征方法、实验拓展等多个方面进行了比较和归纳,并对其设计理念和教学特色进行了综述。
