The Ni@Au core-shell nanoparticles had been successfully synthesized from aqueous solution by one-step route at room temperature. The Ni@Au nanoparticles can be an excellent catalyst for Ullmann reaction. The advantag...The Ni@Au core-shell nanoparticles had been successfully synthesized from aqueous solution by one-step route at room temperature. The Ni@Au nanoparticles can be an excellent catalyst for Ullmann reaction. The advantage of Ni@Au is that the catalyst does not need additional reducing agents. The Au shell can effectively protect the Ni core from oxidation. The Ni core and Au shell have both composited in structure and cooperated in function.展开更多
Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capa...Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.展开更多
The nanostructured mesoporous Pd/MCM-41 catalyst was prepared by impregnation.This catalyst exhibited high activity and selectivity to piphenyl during Ullmann coupling reaction of iodobenzene.With Pd loading of 12%,th...The nanostructured mesoporous Pd/MCM-41 catalyst was prepared by impregnation.This catalyst exhibited high activity and selectivity to piphenyl during Ullmann coupling reaction of iodobenzene.With Pd loading of 12%,the biphenyl yield may reach 50%,showing its good potential to match the homogeneous catalyst in traditional Ullmann coupling reactions.Based on BET and XRD etc.characterizations,the relationship between the excellent catalytic properties of the Pd/MCM-41 and its structural characteristics was discussed briefly.展开更多
BAY-069是目前体外活性最强的支链氨基酸转氨酶1(BCAT1)抑制剂,但其报道的合成路线存在原料成本较高、总收率极低和中间体结构表征不充分等缺点。本研究基于已有合成路线,重点对其合成工艺中的Ullmann偶联反应进行了系统优化。以1-硝基...BAY-069是目前体外活性最强的支链氨基酸转氨酶1(BCAT1)抑制剂,但其报道的合成路线存在原料成本较高、总收率极低和中间体结构表征不充分等缺点。本研究基于已有合成路线,重点对其合成工艺中的Ullmann偶联反应进行了系统优化。以1-硝基萘(1)为起始原料,经过7步反应和手性色谱柱手性拆分合成目标化合物BAY-069。所有中间体和目标化合物均经1 H NMR,13 C NMR和HR-MS表征。以Ullmann偶联反应为主要优化步骤的路线,其优化后的总收率为11.0%(3b→(±)-BAY-069),是原总收率1.6%(3a→(±)-BAY-069)的6.9倍。展开更多
对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2...对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。展开更多
基金Supported by the Natural Science Foundation of Jiangsu Province (BK2009678)
文摘The Ni@Au core-shell nanoparticles had been successfully synthesized from aqueous solution by one-step route at room temperature. The Ni@Au nanoparticles can be an excellent catalyst for Ullmann reaction. The advantage of Ni@Au is that the catalyst does not need additional reducing agents. The Au shell can effectively protect the Ni core from oxidation. The Ni core and Au shell have both composited in structure and cooperated in function.
基金Supported by the National Natural Science Foundation of China(21176038,21576044,21536002)the Science Fund for Creative Research Groups of the National Natural Science Foundation of China(21421005)the Dalian University of Technology Innovation Team(DUT2013TB07)
文摘Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.
文摘The nanostructured mesoporous Pd/MCM-41 catalyst was prepared by impregnation.This catalyst exhibited high activity and selectivity to piphenyl during Ullmann coupling reaction of iodobenzene.With Pd loading of 12%,the biphenyl yield may reach 50%,showing its good potential to match the homogeneous catalyst in traditional Ullmann coupling reactions.Based on BET and XRD etc.characterizations,the relationship between the excellent catalytic properties of the Pd/MCM-41 and its structural characteristics was discussed briefly.
文摘BAY-069是目前体外活性最强的支链氨基酸转氨酶1(BCAT1)抑制剂,但其报道的合成路线存在原料成本较高、总收率极低和中间体结构表征不充分等缺点。本研究基于已有合成路线,重点对其合成工艺中的Ullmann偶联反应进行了系统优化。以1-硝基萘(1)为起始原料,经过7步反应和手性色谱柱手性拆分合成目标化合物BAY-069。所有中间体和目标化合物均经1 H NMR,13 C NMR和HR-MS表征。以Ullmann偶联反应为主要优化步骤的路线,其优化后的总收率为11.0%(3b→(±)-BAY-069),是原总收率1.6%(3a→(±)-BAY-069)的6.9倍。
文摘对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。
