Cobalt‐Catalyzed Radical Hydroamination of Alkenes with
<i>N</i>
‐Fluorobenzenesulfonimides
作者:Tao Qin、Guowei Lv、Qi Meng、Ge Zhang、Tao Xiong、Qian Zhang
DOI:10.1002/anie.202110178
日期:2021.12
N-fluorobenzenesulfonimide (NFSI) and its analogues as both nitrogen source and oxidant was successfully disclosed. A variety of alkenes, including aliphatic alkenes, styrenes, α, β-unsaturated esters, amides, acids, as well as enones, were all compatible to provide desired amination products. Mechanistic experiments suggest that the reaction underwent a metal-hydride-mediated hydrogen atom transfer (HAT) with alkene
成功地公开了使用 Co(salen) 作为催化剂、N-氟苯磺酰亚胺 (NFSI) 及其类似物作为氮源和氧化剂的烯烃的有效和通用自由基加氢胺化。各种烯烃,包括脂肪族烯烃、苯乙烯、α, β-不饱和酯、酰胺、酸以及烯酮,都可以提供所需的胺化产物。机理实验表明,该反应与烯烃进行了金属氢化物介导的氢原子转移 (HAT),然后是关键的催化剂控制原位生成的有机钴 (IV) 物质和氮基亲核试剂之间的类 SN 2 途径。此外,借助改性手性钴 (II)-salen 催化剂,还实现了前所未有的不对称版本,具有良好到出色的对映控制水平。