Dhital Raghu N, Sen Abhijit, Hu Hao, Ishii Rikako, Sato Takuma, Yashiroda Yoko, Kimura Hiromi, Boone Charles, Yoshida Minoru, Futamura Yushi, Hirano Hiroyuki, Osada Hiroyuki, Hashizume Daisuke, Uozumi Yasuhiro, Yamada Yoichi M A
Green Nanocatalysis Research Team, RIKEN Center for Sustainable Resource Science, Wako, Saitama 351-0198, Japan.
Molecular Ligand Target Research Team, RIKEN Center for Sustainable Resource Science, Wako, Saitama 351-0198, Japan.
ACS Omega. 2022 Jul 1;7(28):24184-24189. doi: 10.1021/acsomega.2c01092. eCollection 2022 Jul 19.
In this study, a phenylboronic ester-activated aryl iodide-selective Buchwald-Hartwig-type amination was developed. When the reaction of aryl iodides and aryl/aliphatic amines using Ni(acac) is carried out in the presence of phenylboronic ester, the Buchwald-Hartwig-type amination proceeds smoothly to afford the corresponding amines in high yields. This reaction does not proceed in the absence of phenylboronic ester. A wide variety of aryl iodides can be applied in the presence of aryl chlorides and bromides, which remain intact during the reaction. The mechanistic studies of this reaction suggest that the phenylboronic ester acts as an activator for the amines to form the ″ate complex″. Chemical kinetics studies show that the reaction of aryl iodides, base, and Ni(acac) follows first-order kinetics, while that of amines and phenylboronic ester follows zero-order kinetics. The bioactivity screening of the corresponding products showed that some amination products exhibit antifungal activity.
在本研究中，开发了一种苯基硼酸酯活化的芳基碘选择性布赫瓦尔德-哈特维希型胺化反应。当在苯基硼酸酯存在下，使用Ni(acac)进行芳基碘与芳基/脂肪族胺的反应时，布赫瓦尔德-哈特维希型胺化反应顺利进行，以高产率得到相应的胺。在没有苯基硼酸酯的情况下，该反应不发生。在芳基氯和溴存在下，可以应用多种芳基碘，它们在反应过程中保持不变。该反应的机理研究表明，苯基硼酸酯作为胺的活化剂形成“酸根络合物”。化学动力学研究表明，芳基碘、碱和Ni(acac)的反应遵循一级动力学，而胺和苯基硼酸酯的反应遵循零级动力学。相应产物的生物活性筛选表明，一些胺化产物具有抗真菌活性。
