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。