Zhang Guofu, Ma Danting, Zhao Yiyong, Zhang Guihua, Mei Guangyao, Lyu Jinghui, Ding Chengrong, Shan Shang
College of Chemical Engineering Zhejiang University of Technology Hangzhou 310014 P. R. China.
Zhejiang Hongyuan Pharmaceutical Co. Ltd Taizhou 317016 P. R. China.
ChemistryOpen. 2018 Nov 13;7(11):885-889. doi: 10.1002/open.201800196. eCollection 2018 Nov.
Aqueous ammonia (NH⋅HO) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with -OH, -NO, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
已证明氨水（NH₃·H₂O）作为最简单的含氮配体，能在水中空气氛围下有效促进铜催化的选择性醇氧化反应。一系列具有不同电子和空间性质的醇被选择性氧化为醛，产率高达95%。值得注意的是，通过在纯水中增加氨水的量，还能以良好至优异的产率实现芳基腈的专一性生成。此外，该催化体系对官能团具有高度耐受性，-OH、-NO₂、酯基和杂芳基均能适应反应条件。这种一锅法绿色氧化方案为从市售醇选择性制备醛或腈提供了一条重要的合成路线。
