Manganese Catalysts with Molecular Recognition Functionality for Selective Alkene Epoxidation

被引：30

作者：

Hull, Jonathan F. ^{[1
]}

Sauer, Effiette L. O. ^{[1
]}

Incarvito, Christopher D. ^{[1
]}

Faller, J. W. ^{[1
]}

Brudvig, Gary W. ^{[1
]}

Crabtree, Robert H. ^{[1
]}

机构：

[1] Yale Univ, Dept Chem, New Haven, CT 06511 USA

来源：

INORGANIC CHEMISTRY | 2009年 / 48卷 / 02期

基金：

加拿大自然科学与工程研究理事会;

关键词：

CYTOCHROME-P-450 MODEL COMPOUNDS; ARTIFICIAL CYTOCHROME-P-450; SHAPE SELECTIVITY; OXYGEN-TRANSFER; HYDROCARBON FUNCTIONALIZATION; ALKANE HYDROXYLATION; OLEFIN EPOXIDATION; BETA-CYCLODEXTRIN; METAL-COMPLEXES; SYSTEM;

D O I：

10.1021/ic8013464

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Selective epoxidation of alkenes is possible with a new manganese porphyrin catalyst, C-PMR, that uses hydrogen bonding between the carboxylic acid on the substrate molecule and a Kemp's triacid unit. For two out of three olefin substrates employed, molecular recognition prevents the unselective oxidation of C-H bonds, and directs oxidation to the olefin moiety, giving only epoxide products. Weak diastereoselectivity is observed in the epoxide products, suggesting that molecular recognition affects the orientation of the catalyst-bound substrate. The previously reported manganese terpyridine complex C-TMR is shown to be a superior epoxidation catalyst to the porphyrin catalyst C-PMR. Good conversion of 2-cyclopentene acetic acid (substrate S2) with C-PMR is consistent with molecular modeling, which indicates a particularly good substrate/catalyst match. Evidence suggests that hydrogen bonding between the substrate and the catalyst is critical in this system.

引用

页码：488 / 495

页数：8

共 51 条

[1] Dendrimer-metalloporphyrins: Synthesis and catalysis [J].