芳烃醛氧化为酯：硫酸盐自由基氧化还原体系。

Oxidation of Aromatic Aldehydes to Esters: A Sulfate Radical Redox System.

机构信息

Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences , Beijing 100190, PR China.

College of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences , Beijing 100049, PR China.

出版信息

J Org Chem. 2017 Feb 3;82(3):1591-1599. doi: 10.1021/acs.joc.6b02775. Epub 2017 Jan 23.

DOI:10.1021/acs.joc.6b02775

PMID:28111951

Abstract

A mild oxidative esterification of various aromatic aldehydes by sulfate radical redox system was presented. In the reaction pathway exploration, the transiency of MeOSO was disclosed, which was generated from esterification between the in situ generated HSO and MeOH, a rate-limiting step in the process. More importantly, the selectivity-controlling step was represented by the subsequent nucleophilic displacement between MeOSO and aldehydes. The ionic oxidant 1a ((NH)SO) with more N-H numbers in the cation, as compared with 1c ((n-BuN)SO) and 1d ((PyH)SO), has better performance in the oxidative esterification of aldehydes.

摘要

提出了一种硫酸盐自由基氧化还原体系温和氧化酯化各种芳香醛的方法。在反应途径的探索中，揭示了 MeOSO 的瞬态性，它是由原位生成的 HSO 和 MeOH 之间的酯化反应生成的，这是该过程的速率限制步骤。更重要的是，随后 MeOSO 和醛之间的亲核取代反应代表了选择性控制步骤。与 1c((n-BuN)SO)和 1d((PyH)SO)相比，阳离子中具有更多 N-H 数的离子氧化剂 1a((NH)SO)在醛的氧化酯化中具有更好的性能。