Aromatic and olefinic C–H alkenylation by catalysis with spirocyclic NHC Ru(Ⅳ) pincer complex  

作　　者：Heng Cai Yong-Qiang Tu Ka Lu Qi-Long Chen Fu-Min Zhang Xiao-Ming Zhang Yuan-Jiang Pan Zhi-Bo Yan 

机构地区：[1]State Key Laboratory of Applied Organic Chemistry&College of Chemistry and Chemical Engineering,Lanzhou University,Lanzhou 730000,China [2]School of Chemistry and Chemical Engineering,Frontiers Science Center for Transformative Molecules,Shanghai Jiao Tong University,Shanghai 200240,China [3]Department of Chemistry,Zhejiang University,Hangzhou 310027,China

出　　处：《Science China Chemistry》2023年第10期2791-2796,共6页中国科学（化学英文版）

基　　金：suported by the National Natural Science Foundation of China (2187,1117, 91956203);the “111” Program of Minister of Education, Beijing National Laboratory for Molecular Sciences (BNLMS202109);the Science and Technology Commission of Shanghai Municipality (19JC1430100)。

摘　　要：Catalyst innovation lies at the heart of transition-metal-catalyzed reaction development. In this article, we have explored the C(sp2)–H alkenylation activity with novel spirocyclic N-heterocyclic carbene(NHC)-based cyclometalated ruthenium pincer catalyst system, SNRu-X. After screening catalyst and condition, a high valent Ru(Ⅳ) dioxide(X = O_(2)) species has demonstrated superior reactivity in the catalytic alkenylation of aromatic and olefinic C–H bonds with unactivated alkenyl bromides and triflates. This reaction has achieved the easy construction of a wide range of(hetero)aromatic alkenes and dienes, in good to excellent yields with exclusive selectivity. Preliminary mechanistic studies indicate that this reaction may proceed through a single electron transfer(SET) triggered oxidative addition, by doing so, providing valuable complementary to classical alkenylation reactions that are dependent on activated alkenyl precursors.

关 键 词：transitionmetal catalysis spirocyclic NHC-Ru pincer catalyst C-H alkenylation single electron transfer pathway unactivated alkenyl bromides and triflates 

分 类 号：O621.251[理学—有机化学]