Lee Geun Seok, Hong Soon Hyeok
Department of Chemistry , College of Natural Science , Seoul National University , 1 Gwanak-ro , Seoul 08826 , South Korea . Email:
Chem Sci. 2018 Jun 11;9(26):5810-5815. doi: 10.1039/c8sc01827h. eCollection 2018 Jul 14.
An unprecedented utilization of triplet excited enones in Ni-catalysis enabled a formal Giese addition of C(sp)-H nucleophiles. This mechanism-based approach has greatly widened the reaction scope, allowing the synthesis of previously inaccessible structures. In this process, the enone diradical acted as two distinct reaction centers, participating in both metalation and hydrogen atom transfer, ultimately furnishing a range of formal Giese addition products in a highly general context. This reaction provides complementary access to traditional 1,4-addition reactions of enones, with a future perspective to develop triplet diradical-based transition metal catalysis.
在镍催化中对三重态激发烯酮的前所未有的应用实现了C(sp)-H亲核试剂的形式上的吉泽加成。这种基于机理的方法极大地拓宽了反应范围，使得能够合成以前无法获得的结构。在这个过程中，烯酮双自由基充当两个不同的反应中心，参与金属化和氢原子转移，最终在非常普遍的情况下提供一系列形式上的吉泽加成产物。该反应为烯酮的传统1,4-加成反应提供了补充途径，有望发展基于三重态双自由基的过渡金属催化。
