Mechanism of Cobalt-Porphyrin-Catalyzed Aziridination

被引：57

作者：

Hopmann, Kathrin H.

Ghosh, Abhik ^{[1
]}

机构：

[1] Univ Tromso, Ctr Theoret & Computat Chem, N-9037 Tromso, Norway

来源：

ACS CATALYSIS | 2011年 / 1卷 / 06期

关键词：

cobalt; porphyrin; nitrene; amination; aziridination; rebound mechanism; SPIN-STATE ENERGETICS; ELECTRONIC-STRUCTURE; OLEFIN AZIRIDINATION; ARYL AZIDES; COMPLEXES; IMIDO; AMINATION; VALENT; IRON;

D O I：

10.1021/cs1001114

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：

Density functional theory (DFT; OLYP) calculations clearly indicate the I involvement of a cobalt nitrene in cobalt-porphyrin-catalyzed alkene aziridinations, as well as in allylic aminations. The transition state for the cobalt-nitrene-alkene interaction May be described as triradicaloid. A subsequent carbon radical, if it exists at all as an intermediate, collapses in an essentially barrierless manner to the aziridine product.

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收藏

页码：597 / 600

页数：4

相关论文

共 29 条

[1]

[Anonymous], 2006, ANGEW CHEM

[2] Allylic amination and aziridination of olefins by aryl azides catalyzed by Co II(tpp):: A synthetic and mechanistic study [J].

Caselli, Alessandro ;

Gallo, Emma ;

Fantauzzi, Simone ;

Morlacchi, Simona ;

Ragaini, Fabio ;

Cenini, Sergio .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2008, 19 (19) :3009-3019

[3] Chiral porphyrin complexes of cobalt(II) and ruthenium(II) in catalytic cyclopropanation and amination reactions [J].

Caselli, Alessandro ;

Gallo, Emma ;

Ragaini, Fabio ;

Ricatto, Federica ;

Abbiati, Giorgio ;

Cenini, Sergio .

INORGANICA CHIMICA ACTA, 2006, 359 (09) :2924-2932

[4] Electronic structure of trigonal-planar transition-metal-imido complexes: Spin-state energetics, spin-density profiles, and the remarkable performance of the OLYP functional [J].

Conradie, Jeanet ;

Ghosh, Abhik .

JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2007, 3 (03) :689-702

[5] Electronic Structure of an Iron-Porphyrin-Nitrene Complex [J].

Conradie, Jeanet ;

Ghosh, Abhik .

INORGANIC CHEMISTRY, 2010, 49 (01) :243-248

[6] 'Carbene Radicals' in CoII(por)-Catalyzed Olefin Cyclopropanation [J].

Dzik, Wojciech I. ;

Xu, Xue ;

Zhang, X. Peter ;

Reek, Joost N. H. ;

de Bruin, Bas .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (31) :10891-10902

[7] The (porphyrin)ruthenium-catalyzed aziridination of olefins using aryl azides as nitrogen sources [J].

Fantauzzi, Simone ;

Gallo, Emma ;

Caselli, Alessandro ;

Piangiolino, Cristiana ;

Ragaini, Fabio ;

Cenini, Sergio .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2007, 2007 (36) :6053-6059

[8] Nitrene transfer reactions mediated by metallo-porphyrin complexes [J].

Fantauzzi, Simone ;

Caselli, Alessandro ;

Gallo, Emma .

DALTON TRANSACTIONS, 2009, (28) :5434-5443

[9] Cobalt-catalyzed efficient aziridination of alkenes [J].

Gao, GY ;

Harden, JD ;

Zhang, XP .

ORGANIC LETTERS, 2005, 7 (15) :3191-3193

[10]

Handy NC, 2001, MOL PHYS, V99, P403, DOI 10.1080/00268970010018451