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一种用于未活化烯烃、烷烃和醇类的通用氧化反应的锰基催化剂体系。

A manganese-based catalyst system for general oxidation of unactivated olefins, alkanes, and alcohols.

作者信息

Verspeek Dennis, Ahrens Sebastian, Wen Xiandong, Yang Yong, Li Yong-Wang, Junge Kathrin, Beller Matthias

机构信息

Leibniz-Institute für Katalyse e.V., Albert-Einstein-Straße 29a, 18059 Rostock, Germany.

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, China.

出版信息

Org Biomol Chem. 2024 Mar 27;22(13):2630-2642. doi: 10.1039/d4ob00155a.

Abstract

Non-noble metal-based catalyst systems consisting of inexpensive manganese salts, picolinic acid and various heterocycles enable epoxidation of the challenging (terminal) unactivated olefins, selective C-H oxidation of unactivated alkanes, and O-H oxidation of secondary alcohols with aqueous hydrogen peroxide. In the presence of the generated optimal manganese catalyst, epoxides are generated with up to 81% yield from alkenes and ketone products with up to 51% yield from unactivated alkanes. This convenient protocol allows the formation of the desired products under ambient conditions (room temperature, 1 bar) by employing only a slight excess of hydrogen peroxide with 2,3-butadione as a sub-stoichiometric additive.

摘要

由廉价的锰盐、吡啶甲酸和各种杂环组成的非贵金属基催化剂体系能够实现具有挑战性的(末端)未活化烯烃的环氧化、未活化烷烃的选择性C-H氧化以及仲醇与过氧化氢水溶液的O-H氧化。在生成的最佳锰催化剂存在下,烯烃生成环氧化物的产率高达81%,未活化烷烃生成酮产物的产率高达51%。该简便方法通过仅使用略微过量的过氧化氢并以2,3-丁二酮作为亚化学计量添加剂,可在环境条件(室温,1巴)下形成所需产物。

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