Catalytic sulfoxidation and epoxidation with a Mn(III) triazacorrole: Evidence for a "third oxidant" in high-valent porphyrinoid oxidations

被引：156

作者：

Wang, SHL ^{[1
]}

Mandimutsira, BS ^{[1
]}

Todd, R ^{[1
]}

Ramdhanie, B ^{[1
]}

Fox, JP ^{[1
]}

Goldberg, DP ^{[1
]}

机构：

[1] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 01期

关键词：

D O I：

10.1021/ja038951a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction between (TBP)8(Cz)Mn(III) (1) and the oxygen atom donors iodosylbenzene (PhIO) or p-cyanodimethylaniline-N-oxide (CDMANO) leads to the manganese(V)-oxo complex (TBP)8(Cz)Mn(V)≡O (2), which has been isolated and characterized previously. Under catalytic conditions with 1 as added catalyst and PhIO as oxidant, both sulfoxidation of PhSMe and epoxidation of cis-stilbene is observed, whereas with CDMANO no sulfoxidation takes place, suggesting that 2 is not the active oxidant. Examination of the independent reactivity of isolated 2 toward PhSMe and cis-stilbene supports this conclusion. A mechanism which relies on a novel type of oxidant involving Lewis acid activation of PhIO by the Mn(V)-oxo complex 2 accounts for these observations and is confirmed by 18O-labeling experiments. Copyright © 2004 American Chemical Society.

引用

页码：18 / 19

页数：2

共 17 条

[1] cis-stilbene and (1α,2β,3α)-(2-ethenyl-3-methoxycyclopropyl)benzene as mechanistic probes in the MnIII(salen)-catalyzed epoxidation:: Influence of the oxygen source and the counterion on the diastereoselectivity of the competitive concerted and radical-type oxygen transfer [J].

Adam, W ;

Roschmann, KJ ;

Saha-Möller, CR ;

Seebach, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (18) :5068-5073

[2] Multiple active oxidants in cytochrome P-450 model oxidations [J].

Collman, JP ;

Chien, AS ;

Eberspacher, TA ;

Brauman, JI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (45) :11098-11100

[3]

Gross Z, 2000, ANGEW CHEM INT EDIT, V39, P4045, DOI 10.1002/1521-3773(20001117)39:22<4045::AID-ANIE4045>3.0.CO

[4]

2-P

[5] First synthesis of perfluorinated corrole and its Mn=O complex [J].

Liu, HY ;

Lai, TS ;

Yeung, LL ;

Chang, CK .

ORGANIC LETTERS, 2003, 5 (05) :617-620

[6] ACYLPEROXO-IRON(III) PORPHYRIN COMPLEXES - A NEW ENTRY OF POTENT OXIDANTS FOR THE ALKENE EPOXIDATION [J].

MACHII, K ;

WATANABE, Y ;

MORISHIMA, I .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (25) :6691-6697

[7] Aerobic oxidations catalyzed by chromium corroles [J].

Mahammed, A ;

Gray, HB ;

Meier-Callahan, AE ;

Gross, Z .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (05) :1162-1163

[8] A stable manganese(V)-oxo corrolazine complex [J].

Mandimutsira, BS ;

Ramdhanie, B ;

Todd, RC ;

Wang, HL ;

Zareba, AA ;

Czemuszewicz, RS ;

Goldberg, DP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (51) :15170-15171

[9]

McLain JL, 2000, BIOMIMETIC OXIDATIONS CATALYZED BY TRANSITION METAL COMPLEXES, P91, DOI 10.1142/9781848160699_0003

[10] Reversible formation of iodosylbenzene-iron porphyrin intermediates in the reaction of oxoiron(IV) porphyrin π-cation radicals and iodobenzene [J].

Nam, W ;

Choi, SK ;

Lim, MH ;

Rohde, JU ;

Kim, I ;

Kim, J ;

Kim, C ;

Que, L .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (01) :109-111

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