Non-heme iron catalysis in C=C, C-H, and CH2 oxidation reactions. Oxidative transformations on terpenoids catalyzed by Fe(bpmen)(OTf)2

被引：29

作者：

Clemente-Tejeda, David ^{[1
]}

Lopez-Moreno, Alejandro ^{[1
]}

Bermejo, Francisco A. ^{[1
]}

机构：

[1] Univ Salamanca, Dept Quim Organ, E-37008 Salamanca, Spain

来源：

TETRAHEDRON | 2013年 / 69卷 / 14期

关键词：

Oxidation; Fe(bpmen)(OTf)(2); Monoterpenes; Magnus lactone; Cytochrome P-450; HYDROGEN-PEROXIDE; CIS-DIHYDROXYLATION; OLEFIN EPOXIDATION; ASYMMETRIC DIHYDROXYLATION; SATURATED-HYDROCARBONS; ALKANE HYDROXYLATION; PORPHYRIN COMPLEXES; DIOXYGEN ACTIVATION; INSERTION REACTIONS; ZINC(II) COMPLEXES;

D O I：

10.1016/j.tet.2013.02.013

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The oxidation of terpene olefins with hydrogen peroxide in the presence of the non-hemo catalyst 5a afforded mixtures of epoxides whose composition was dependent upon the oxidation protocol used in each case. With terpenoid enones, the mixtures obtained evolved from clean epoxidation of alpha-ionone 23 to the clean allylic oxidation of damascone 28 due to the progressive deactivation of the electron density on the double bonds present in this series. The oxidation of bicyclic and tricyclic terpenoids afforded oxidation products coming from epoxidation, to olefin degradation, methyne and methylene activation products. Probably, the most attractive result was the synthesis of the Magnus lactone 46, from the tricyclic ether 45, with 88% yield and 100% conversion. (C) 2013 Elsevier Ltd. All rights reserved.

引用

页码：2977 / 2986

页数：10

共 98 条

[11] Synthesis of iron(II), manganese(II), cobalt(II) and ruthenium(II) complexes containing tridentate nitrogen ligands and their application in the catalytic oxidation of alkanes [J].

Britovsek, GJP ;

England, J ;

Spitzmesser, SK ;

White, AJP ;

Williams, DJ .

DALTON TRANSACTIONS, 2005, (05) :945-955

[12]

Britovsek GJP, 2006, DALTON T, P1399, DOI 10.1039/b513886h

[13] Non-heme lron(II) complexes containing tripodal tetradentate nitrogen ligands and their application in alkane oxidation catalysis [J].

Britovsek, GJP ;

England, J ;

White, AJP .

INORGANIC CHEMISTRY, 2005, 44 (22) :8125-8134

[14] Iron(II) complexes with bio-inspired N,N,O ligands as oxidation catalysts:: Olefin epoxidation and cis-dihydroxylation [J].

Bruijnincx, Pieter C. A. ;

Buurmans, Inge L. C. ;

Gosiewska, Silvia ;

Moelands, Marcel A. H. ;

Lutz, Martin ;

Spek, Anthony L. ;

van Koten, Gerard ;

Gebbink, Robertus J. M. Klein .

CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (04) :1228-1237

[15] Mononuclear non-heme iron enzymes with the 2-His-1-carboxylate facial triad: recent developments in enzymology and modeling studies [J].

Bruijnincx, Pieter C. A. ;

van Koten, Gerard ;

Gebbink, Robertus J. M. Klein .

CHEMICAL SOCIETY REVIEWS, 2008, 37 (12) :2716-2744

[16] Biomimetic Trispyrazolylborato Iron Complexes [J].

Burzlaff, Nicolai .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (31) :5580-5582

[17] RING-OPENING OF ALPHA-PINENE EPOXIDE [J].

CARR, G ;

DOSANJH, G ;

MILLAR, AP ;

WHITTAKER, D .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1994, (07) :1419-1422

[18] Oxidation of natural compounds catalyzed by Mn(III) porphyrin complexes [J].

Cavaleiro, JAS ;

Nascimento, GMSFC ;

Neves, MGPMS ;

Pinto, MT ;

Silvestre, AJD ;

Vicente, MGH .

TETRAHEDRON LETTERS, 1996, 37 (11) :1893-1896

[19] Spin state tuning of non-heme iron-catalyzed hydrocarbon oxidations:: participation of FeIII-OOH and FeV=O intermediates [J].

Chen, K ;

Costas, M ;

Que, L .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (05) :672-679

[20] Stereospecific alkane hydroxylation by non-heme iron catalysts:: Mechanistic evidence for an FeV=O active species [J].

Chen, K ;

Que, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (26) :6327-6337

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