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| 1 | SERS-HPLC联用技术对邻氨基苯硫酚与邻碘苯甲酰氯反应的监测显示文摘通过表面增强拉曼光谱(SERS)与高效液相色谱(HPLC)联用开展了在线监测催化剂对邻氨基苯硫酚(OATP)与邻碘苯甲酰氯反应的影响.结果表明,无催化剂时反应产物为1b{S-[2-(2碘苯甲酰氨基)苯基]-2-碘代苯硫酸盐}和2b{N,N′-[二硫(2,1-亚苯基)]二(2-碘苯甲酰胺)},在醋酸铜催化下生成3b{10-(2-碘苯甲酰基)二苯并[b,f][1,4]硫氮杂-11(10H)-酮};无催化剂条件下经历亲核取代反应及硫自由基耦合的过程,在醋酸铜催化下产物1b的结构发生变异生成3b.所得结果与核磁质谱等常规非现场技术解析结构一致. | 张辉 张晨杰 徐敏敏 袁亚仙 姚建林 | 2020 | 高等学校化学学报2020，41，11： | 1 |
| 2 | A theoretical study on the mechanisms of intermolecular hydroacylation of aldehyde catalyzed by neutral and cationic rhodium complexes显示文摘In this paper, we used density functional theory(DFT) computations to study the mechanisms of the hydroacylation reaction of an aldehyde with an alkene catalyzed by Wilkinson's catalyst and an organic catalyst 2-amino-3-picoline in cationic and neutral systems. An aldehyde's hydroacylation includes three stages: the C–H activation to form rhodium hydride(stage I), the alkene insertion into the Rh–H bond to give the Rh-alkyl complex(stage II), and the C–C bond formation(stage III). Possible pathways for the hydroacylation originated from the trans and cis isomers of the catalytic cycle. In this paper, we discussed the neutral and cationic pathways. The rate-determining step is the C–H activation step in neutral system but the reductive elimination step in the cationic system. Meanwhile, the alkyl group migration-phosphine ligand coordination pathway is more favorable than the phosphine ligand coordination-alkyl group migration pathway in the C–C formation stage. Furthermore, the calculated results imply that an electron-withdrawing group may decrease the energy barrier of the C–H activation in the benzaldehyde hydroacylation. | WANG Min ZHANG Xin CHEN Zhuo TANG YanHui LEI Ming | 2014 | Science China Chemistry2014，57，9： | 0 |
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