20056-64-8Relevant academic research and scientific papers
Nickel-Catalyzed Decarboxylative Alkylation of Aryl Iodides with Anhydrides
Chen, Hui,Hu, Lu,Ji, Wenzhi,Yao, Licheng,Liao, Xuebin
, p. 10479 - 10485 (2018/10/24)
We present the anhydride-based decarboxylative alkylation of aryl iodides catalyzed by nickel. This method of decarboxylative coupling works with a broad scope of aliphatic carboxylic anhydrides and tolerates synthetically useful aromatic substituents. Assisted by a redox system of pyridine N-oxide and zinc additives, the current reaction occurs under mild conditions and without the assistance of photocatalyst. Notably, this method features high chemoselectivity toward alkyl migration with mixed aliphatic/aromatic anhydrides. Thus, it provides a powerful synthetic tool to modify high-valued aliphatic carboxylic acids by converting them into mixed anhydrides using readily available aryl carboxylic acids such as p-toluic acid. We propose a catalytic cycle that involves the key steps of free radical-based decarboxylation and subsequent alkyl transfer to nickel that precedes an oxidatively induced C-C reductive elimination from Ni(III).
Iron(III)-Catalyzed Ortho-Preferred Radical Nucleophilic Alkylation of Electron-Deficient Arenes
Yu, Fei,Wang, Ting,Zhou, Huan,Li, Yajun,Zhang, Xinhao,Bao, Hongli
supporting information, p. 6538 - 6541 (2017/12/26)
The untraditional iron-catalyzed, ortho-preferred, radical alkylation of electron-deficient (hetero)arenes is reported. A variety of electron-deficient arenes were shown to react with various primary alkyl sources, producing the alkylated (hetero)arenes in good yields. This reaction might be an alkyl radical, nucleophilic aromatic substitution reaction, rather than the traditional electrophilic Friedel-Crafts reaction. HOMO-LUMO analysis and DFT studies on the key transition states underlying the regioselectivity are consistent with the observed reactions and the conclusions.
