Wang Peng-Zi, He Bin-Qing, Cheng Ying, Chen Jia-Rong, Xiao Wen-Jing
CCNU-uOttawa Joint Research Centre, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China.
Org Lett. 2019 Sep 6;21(17):6924-6929. doi: 10.1021/acs.orglett.9b02535. Epub 2019 Aug 22.
A light-driven, metal-free, and iminyl radical-mediated ring-opening C-C bond cleavage/addition cascade of -4-methoxybenzyl oxime ethers and alkenes is described for the first time. The reaction shows a broad substrate scope and high functional group compatibility with both components, giving the corresponding valuable oxo nitriles in generally good yields. Key to the success of this protocol is the generation of cyclic iminyl radicals from the -4-methoxybenzyl oxime ethers via a photocatalytic hydrogen atom transfer (HAT) process. The proposed main pathway is also supported by the preliminary mechanistic studies.
首次报道了一种光驱动、无金属且由亚胺基自由基介导的对甲氧基苄基肟醚与烯烃的开环碳-碳键裂解/加成串联反应。该反应对两种底物都具有广泛的底物范围和高官能团兼容性，通常能以良好的产率得到相应有价值的氧代腈。该方法成功的关键是通过光催化氢原子转移（HAT）过程从对甲氧基苄基肟醚生成环状亚胺基自由基。初步的机理研究也支持所提出的主要反应途径。
