文献类型：期刊文献

英文题名：Direct insertion into the C-C bond of unactivated ketones with NaH-mediated aryne chemistry

作者：Luo, Fa[1,2,3,4];Li, Chen-Long[5];Ji, Peng[6,7];Zhou, Yuxin[1,2];Gui, Jingjing[1,2];Chen, Lingyun[1,2];Yin, Yuejia[1,2];Zhang, Xinyu[3,4];Hu, Yanwei[1,2];Chen, Xiaobei[3,4];Liu, Xuejun[8];Chen, Xiaodong[8];Yu, Zhi-Xiang[5];Wang, Wei[3,4,6,7];Zhang, Shi-Lei[1,2]

机构：[1]Soochow Univ, Jiangsu Key Lab Neuropsychiat Dis, 199 Renai Rd, Suzhou 215123, Jiangsu, Peoples R China;[2]Soochow Univ, Coll Pharmaceut Sci, 199 Renai Rd, Suzhou 215123, Jiangsu, Peoples R China;[3]East China Univ Sci & Technol, Sch Pharm, Shanghai Key Lab New Drug Design, Shanghai Frontiers Sci Ctr Optogenet Tech Cell Met, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Sch Pharm, State Key Lab Bioengn Reactor, Shanghai 200237, Peoples R China;[5]Peking Univ, Coll Chem, Beijing Natl Lab Mol Sci BNLMS, Key Lab Bioorgan Chem & Mol Engn,Minist Educ, Beijing 100871, Peoples R China;[6]Univ Arizona, Dept Pharmacol & Toxicol, 1703 E Mabel St,POB 210207, Tucson, AZ 85721 USA;[7]Univ Arizona, Inst BIO5, 1703 E Mabel St,POB 210207, Tucson, AZ 85721 USA;[8]Shanghai Neutan Pharmaceut Co Ltd, Pudong New Area, Bldg 26,555 Huanqiao Rd, Shanghai, Peoples R China

年份：2023

卷号：9

期号：9

外文期刊名：CHEM

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001150012200001)】；

基金：This work was supported by the National Natural Science Foundation of China (21738002, 22271206, 22071053, and 21933003), the High-Performance Computing Platform of Peking University, PAPD (a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions), the Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism (Shanghai Municipal Education Commission, grant 2021 Sci & Tech 03-28), and the "111"Project of the East China University of Science and Technology.

语种：英文

摘要：Here, we document the reinvention of aryne chemistry with "old"o-diiodoarenes as aryne progenitors. We have established a NaHmediated activation strategy for the generation of highly reactive aryne species in a controlled manner. The resulting arynes can efficiently participate in a C-C s-bond-insertion reaction with unactivated ketones, which is difficult to achieve by existing methods. Density functional theory (DFT) calculations reveal that the two adjacent iodines in o-diiodoarenes play critical roles in the formation of aryne. The nucleophilic attack of hydride to the electrophilic iodine requires that the adjacent iodine act as a directing group to accelerate this process, whereas mono-substituted iodobenzene lacking the neighboring-group participation makes it difficult. The in -situ formed enolates from ketones are proposed to adopt tetrameric aggregates to react with arynes, which accounts for the high regiochemistry for substrates with bulky substituents.