Kolluru Srinivas, Singh Manvendra, Gaskins Bryce, Boskovic Zarko
Department of Medicinal Chemistry, University of Kansas, Lawrence 66045, Kansas.
ACS Catal. 2021 Aug 20;11(16):10351-10361. doi: 10.1021/acscatal.1c03092. Epub 2021 Aug 5.
We report the discovery, development, and mechanism of a nickel-catalyzed annulation reaction between -haloarylimines and electron-poor olefins. The reaction produces two adjacent stereocenters and a free secondary amine. Spirocycles are formed from cyclic imines. We characterized the key oxidative addition intermediate and identified a major path leading to competing homocoupling products. The activation energy of oxidative addition and the rate of oxidative addition complex isomerization were determined. The sensitivity of the reaction to reaction conditions was established in a quantitative manner and both the scope and limitations of the method are presented.
我们报道了一种镍催化的卤代芳基胺与贫电子烯烃之间的环化反应的发现、发展及机理。该反应生成两个相邻的立体中心和一个游离仲胺。螺环由环状亚胺形成。我们对关键的氧化加成中间体进行了表征,并确定了一条导致竞争性均偶联产物的主要途径。测定了氧化加成的活化能和氧化加成络合物异构化的速率。以定量方式确定了该反应对反应条件的敏感性,并介绍了该方法的适用范围和局限性。