Modular ipso/ ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene Cooperative Catalysis.
Modular ipso/ ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene Cooperative Catalysis.
复制标题
DOI：
10.1021/jacs.8b04153
复制
发表时间：
2018-07-11
影响因子：
15
通讯作者：
Dong G
中科院分区：
文献类型：
--
作者：
Dong Z;Lu G;Wang J;Liu P;Dong G
钯/降冰片烯(Pd/NBE)协同催化已成为制备多取代芳烃的有效工具，但其底物范围在很大程度上局限于芳基碘化合物。虽然芳基溴化物被认为是Pd催化交叉偶联反应的标准底物，但它们在Pd/NBE催化中的应用仍然难以捉摸。在这里，我们描述了芳基溴介导的Pd/NBE协同催化的一般方法的发展。通过仔细调整膦配体和猝灭亲核试剂，实现了芳基溴化物的邻胺化、酰化和烷基化反应。重要的是，各种杂芳烃底物也很好地工作，并且可以容忍广泛的官能团。此外，这些方法在连续的交叉偶联/邻位功能化反应、Pd/NBE催化的连续双官能化合成五取代芳香族化合物和两步间位功能化反应中也得到了应用。此外，还通过密度泛函理论探讨了邻胺化反应中配体效应的来源。这一努力有望大大扩展Pd/NBE催化剂在制备复杂芳香族化合物方面的反应范围和合成潜力。
Palladium/norbornene (Pd/NBE) cooperative catalysis has emerged as a useful tool for preparing poly substituted arenes; however, its substrate scope has been largely restricted to aryl iodides. While aryl bromides are considered as standard substrates for Pd-catalyzed cross coupling reactions, their use in Pd/NBE catalysis remains elusive. Here we describe the development of general approaches for aryl bromide-mediated Pd/NBE cooperative catalysis. Through careful tuning the phosphine ligands and quenching nucleophiles, ortho amination, acylation and alkylation of aryl bromides have been realized in good efficiency. Importantly, various heteroarene substrates also work well and a wide range of functional groups are tolerated. In addition, the utility of these methods has been demonstrated in sequential cross coupling/ortho functionalization reactions, consecutive Pd/NBE-catalyzed difunctionalization to construct penta-substituted aromatics and two-step meta functionalization reactions. Moreover, the origin of the ligand effect in ortho amination reactions has been explored through DFT studies. It is expected that this effort would significantly expand the reaction scope and enhance the synthetic potential for Pd/NBE catalysis in preparing complex aromatic compounds.
登录
查看更多内容
影响因子：
5.2
作者：
Catellani, M;Motti, E;Baratta, S
通讯作者：
Baratta, S
影响因子：
1.2
作者：
Clarke, ED;Delaney, JS
通讯作者：
Delaney, JS
影响因子：
2.3
作者：
CATELLANI, M;CHIUSOLI, GP
通讯作者：
CHIUSOLI, GP
钯/降冰片烯介导的芳基碘化物与仲环 O-苯甲酰羟胺和活化末端烯烃的串联 C-H 胺化/C-I 烯基化反应
影响因子：
4.3
作者：
Chen, Zhi-Yuan;Ye, Chang-Qing;Yuan, Jian-Jun
通讯作者：
Yuan, Jian-Jun
影响因子：
5.2
作者：
Blanchot, Mathieu;Candito, David A.;Lautens, Mark
通讯作者：
Lautens, Mark