Characterization of Tunable Radical Metal-Carbenes: Key Intermediates in Catalytic Cyclopropanation

被引：62

作者：

Belof, Jonathan L. ^{[1
,2
]}

Cioce, Christian R. ^{[1
]}

Xu, Xue ^{[1
]}

Zhang, X. Peter ^{[1
]}

Space, Brian ^{[1
]}

Woodcock, H. Lee ^{[1
]}

机构：

[1] Univ S Florida, Dept Chem, Tampa, FL 33620 USA

[2] Lawrence Livermore Natl Lab, Livermore, CA 94550 USA

来源：

ORGANOMETALLICS | 2011年 / 30卷 / 10期

关键词：

HIGHLY ENANTIOSELECTIVE CYCLOPROPANATION; ASYMMETRIC CYCLOPROPANATION; RUTHENIUM PORPHYRIN; CHIRAL PORPHYRIN; INTRAMOLECULAR CYCLOPROPANATIONS; OLEFIN AZIRIDINATION; AMINOBUTYRIC-ACID; PARTIAL AGONIST; BASIS-SETS; ALKENES;

D O I：

10.1021/om2001348

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A new class of radical metal-carbene complex has been characterized as having Fischer-like orbital interactions and adjacent pi acceptor stabilization. Density functional theory along with natural bond orbital analysis and charge decomposition analysis has given insight into the electronics of this catalytic intermediate in an open-shell cobalt-porphyrin, [Co(Por)], system. The complex has a single bond from the metal to the carbene and has radical character with localized spin density on the carbene carbon. In addition, the carbene carbon is found to be nucleophilic and "tunable" through the introduction of different alpha-carbon substituents. Finally, based on these findings, rational design strategies are proposed that should lead to the enhancement of catalytic activity.

引用

页码：2739 / 2746

页数：8

共 85 条

[11] Asymmetric cyclopropanation of styrenes catalyzed by metal complexes of D2-Symmetrical chiral porphyrin:: Superiority of cobalt over iron [J].

Chen, Ying ;

Zhang, X. Peter .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (15) :5931-5934

[12] Theoretical study of the rhenium-alkane interaction in transition metal-alkane σ-complexes [J].

Cobar, Erika A. ;

Khaliullin, Rustam Z. ;

Bergman, Robert G. ;

Head-Gordon, Martin .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2007, 104 (17) :6963-6968

[13]

CUNDARI TR, 1996, REV COMPUTATIONAL CH

[14] INVESTIGATION OF DONOR-ACCEPTOR INTERACTIONS - A CHARGE DECOMPOSITION ANALYSIS USING FRAGMENT MOLECULAR-ORBITALS [J].

DAPPRICH, S ;

FRENKING, G .

JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (23) :9352-9362

[15] Hydrogen-Atom Transfer in Reactions of Organic Radicals with [CoII(por)]• (por = Porphyrinato) and in Subsequent Addition of [Co(H)(por)] to Olefins [J].

de Bruin, Bas ;

Dzik, Wojciech I. ;

Li, Shan ;

Wayland, Bradford B. .

CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (17) :4312-4320

[16]

DEWAR JS, 1951, B SOC CHIM FR, V18, pC71

[17] Well-defined ruthenium olefin metathesis catalysts: Mechanism and activity [J].

Dias, EL ;

Nguyen, ST ;

Grubbs, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (17) :3887-3897

[18]

Doyle M. P., 1998, MODERN CATALYTIC MET

[19] Exceptional Selectivity in Cyclopropanation Reactions Catalyzed by Chiral Cobalt(II)-Porphyrin Catalysts [J].

Doyle, Michael P. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (05) :850-852

[20] HIGH ENANTIOSELECTIVITY IN THE INTRAMOLECULAR CYCLOPROPANATION OF ALLYL DIAZOACETATES USING A NOVEL RHODIUM(II) CATALYST [J].

DOYLE, MP ;

PIETERS, RJ ;

MARTIN, SF ;

AUSTIN, RE ;

OALMANN, CJ ;

MULLER, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (04) :1423-1424

← 1 2 3 4 5 6 7 8 9 →