文献类型：期刊文献

英文题名：Direct Synthesis of Esters from Alkylarenes and Carboxylic Acids: The C-H Bond Dehydroesterification

作者：Zhang, Jin[1];Cao, Jianghan[1];Zhou, Jiabin[1];Zhang, Jie[1];Zhao, Yinglin[1];Zhang, Zhida[1];Liu, Renhua[1,2]

机构：[1]East China Univ Sci & Technol, Sch Pharm, Shanghai 200237, Peoples R China;[2]Engn Res Ctr Pharmaceut Proc Chem, Shanghai 200237, Peoples R China

年份：2023

卷号：88

期号：13

起止页码：9087

外文期刊名：JOURNAL OF ORGANIC CHEMISTRY

收录：;EI(收录号：20232614325848);WOS:【SCI-EXPANDED(收录号:WOS:001008125300001)，CCR-EXPANDED(收录号:WOS:001008125300001)】；

基金：We gratefully acknowledge the National Natural Science Foundation of China (grants 21072055) for financial support of this work.

语种：英文

外文关键词：Aluminum compounds - Carboxylic acids - Doping (additives) - Esters - Hydrogen - Palladium

摘要：Herein, a reaction in which the benzyl C-H bondsof alkylarenesare directly esterified by carboxylic acids to produce benzyl estersin high yields is reported. This reaction is catalyzed by Pd nanoparticles(NPs) on N-doped carbon (CN) composites based ona carbonizing Al-MIL-101(NH2) material, and no oxidantsor hydrogen acceptors are required. Use of o-alkylbenzoicacids as substrates leads to phthalides, whereas with carboxylic acidsand alkylarenes as the feedstock, the reaction produces the benzylesters. These reactions that use readily available alkylarenes insteadof benzyl halides or benzyl alcohols as raw materials for one-stepsynthesis of benzyl esters without oxidants are inherently atom- andstep-efficient. The CN composites and the CN-supported Pd NP catalystswere prepared and are well characterized. The proposed mechanism involvesdehydrogenation of both the carboxylic groups and the benzylic groupsand the transformation of benzylic C-H bond into the C-Obond via hydrogen abstraction from the benzylic group through an organopalladiumintermediate. The kinetic isotope effect (k (H)/k (D) = 2.77) indicated that C(sp(3))-H bond cleavage of the alkane aromatics is the rate-determiningstep.