Oxidant-Controlled C-sp<sup>2</sup>/sp<sup>3</sup>–H Cross-Dehydrogenative Coupling of N-Heterocycles with Benzylamines
作者:Rohit Sharma、Mohd Abdullaha、Sandip B. Bharate
DOI:10.1021/acs.joc.7b00856
日期:2017.9.15
cross-dehydrogenative coupling (CDC) of benzylamines with N-heterocycles having sp2 or sp3 carbon resulted in the formation of C-benzoylated or alkenylated products. Benzoylation of N-heterocycles occurs via (NH4)2S2O8 catalyzed benzoyl radical formation. An oxidative alkenylation of N-heterocycles having C-sp3 carbon (2-methylaza-arenes) occurs via deamination of benzylamine followed by C-sp3-H bond activation
苄基胺与具有sp 2或sp 3碳的N-杂环的氧化剂控制的离子液体介导的交叉脱氢偶联(CDC)导致C-苯甲酰化或烯基化产物的形成。N-杂环的苯甲酰化是通过(NH 4)2 S 2 O 8催化的苯甲酰基基团形成的。具有C-sp 3碳的N-杂环(2-甲基氮杂芳烃)的氧化烯基化反应是通过苄胺的脱氨基反应,然后以高立体选择性进行C-sp 3 -H键活化而进行的。苯甲酰化和烯基化方案均不含金属,绿色,简单,有效,并且可耐受多种官能团。
Nickel-catalyzed electrochemical Minisci acylation of aromatic N-heterocycles with α-keto acids via ligand-to-metal electron transfer pathway
作者:Hang Ding、Kun Xu、Cheng-Chu Zeng
DOI:10.1016/j.jcat.2019.10.030
日期:2020.1
A nickel-catalyzed electrochemical methodology for the Minisci acylation of aromatic electron-deficient heterocycles with α-keto acids has been developed. The reaction is performed in an undivided cell under constant current conditions, featuring broad scope of substrates and avoiding the conventional utilization of silver-based catalysts in conjunction with excess amount of oxidants. Cyclic voltammetric