Oxidation of Alkenes with H2O2 by an in-Situ Prepared Mn(II)/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones in Activating H2O2

被引：40

作者：

Dong, Jia Jia ^{[1
]}

Saisaha, Pattama ^{[1
]}

Meinds, Tim G. ^{[1
]}

Alsters, Paul L. ^{[2
]}

Ijpeij, Edwin G. ^{[2
]}

van Summeren, Ruben P. ^{[2
]}

Mao, Bin ^{[1
]}

Fananas-Mastral, Martin ^{[1
]}

de Boer, Johannes W. ^{[3
]}

Hage, Ronald ^{[3
]}

Feringa, Ben L. ^{[1
]}

Browne, Wesley R. ^{[1
]}

机构：

[1] Univ Groningen, Fac Math & Nat Sci, Stratingh Inst Chem, NL-9747 AG Groningen, Netherlands

[2] DSM Innovat Synth, NL-6160 MD Geleen, Netherlands

[3] Catexel Ltd, BioPartner Ctr Leiden, NL-2333 AL Leiden, Netherlands

来源：

ACS CATALYSIS | 2012年 / 2卷 / 06期

基金：

欧洲研究理事会;

关键词：

manganese; epoxidation; cis-dihydroxylation; hydrogen peroxide; AQUEOUS HYDROGEN-PEROXIDE; MANGANESE(IV) COMPLEX; PERACETIC-ACID; EPOXIDATION; EFFICIENT; OLEFINS; SELECTIVITY; MECHANISM; METHYLTRIOXORHENIUM; ALCOHOLS;

D O I：

10.1021/cs3002226

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A simple, high yielding catalytic method for the multigram scale selective epoxidation of electron-rich alkenes using near-stoichiometric H2O2 under ambient conditions is reported. The system consists of a Mn(II) salt (<0.01 mol %), pyridine-2-carboxylic acid (<0.5 mol %), and substoichiometric butanedione. High TON (up to 300 000) and TOF (up to 40 s(-1)) can be achieved for a wide range of substrates with good to excellent selectivity, remarkable functional group tolerance, and a wide solvent scope. It is shown that the formation of 3-hydroperoxy-3-hydroxybutan-2-one from butanedione, and H2O2 in situ, is central to the activity observed.

引用

页码：1087 / 1096

页数：10

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