Electro-oxidation cross-coupling of primary and secondary alcohols by constructing intermediate-enriched micro-environment  

作　　者：Leitao Xu Cairong Wang Yelin Yao Wei Chen Zhonghuan Zhu Jingcheng Wu Ming Yang Yandong Wu Shuangyin Wang Yuqin Zou 

机构地区：[1]State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha,Hunan,410082,China [2]School of Chemistry and Chemical Engineering,Jishou University,Jishou,416000,China

出　　处：《Science China Chemistry》2023年第8期2408-2415,共8页中国科学（化学英文版）

基　　金：supported by the National Key R&D Program of China(2020YFA0710000);the National Natural Science Foundation of China(22122901);the Provincial Natural Science Foundation of Hunan(2021JJ0008,2021JJ20024,2021RC3054);the Provincial Natural Science Foundation of Hunan(2022JJ40043);Hunan Provincial Innovation Foundation For Postgraduate(CX20220386)。

摘　　要：Electrocatalytic dehydrogenative cross-coupling of various alcohols in aqueous electrolytes functionalizes alcohols to form structurally diverse long-carbon-chain chemicals.However,it remains challenging to achieve the high selectivity because of the high reactivity of involved carbonyl intermediates and different oxidation rates for the alcohols.Herein,the synthesis ofα,β-unsaturated ketones from alcohols was realized by the electro-oxidation cross-coupling in aqueous solutions by a“salting-out”strategy to engineer the micro-environment at electrocatalytic reaction interfaces.Theoretical calculations and electrochemical measurements demonstrated that concentrated local intermediates could inhibit the over-oxidation of alcohols and accelerate the coupling reaction kinetics between the intermediates.This strategy can couple primary and secondary alcohols to formα,β-unsaturated carbonyl compounds with a selectivity of 87% and be easily scaled up to gram scales.This study provides an attractive strategy for broadening the diversity of organic products in electrocatalysis.

关 键 词：electro-oxidation of alcohols CROSS-COUPLING cation effect MICROENVIRONMENT 

分 类 号：TQ203.2[化学工程—有机化工]