Evidence of two-state reactivity in alkane hydroxylation by Lewis-acid bound copper-nitrene complexes

被引：33

作者：

Abram, Sarah-Luise ^{[1
]}

Monte-Perez, Ines ^{[1
]}

Pfaff, Florian Felix ^{[1
]}

Farquhar, Erik R. ^{[2
,3
]}

Ray, Kallol ^{[1
]}

机构：

[1] Humboldt Univ, Inst Chim, D-12489 Berlin, Germany

[2] Case Western Reserve Univ, Ctr Synchrotron Biosci, Upton, NY 11973 USA

[3] Brookhaven Natl Lab, Ctr Prote & Bioinformat, Natl Synchrotron Light Source, Upton, NY 11973 USA

来源：

CHEMICAL COMMUNICATIONS | 2014年 / 50卷 / 69期

关键词：

C-H AMINATION; CATALYTIC MECHANISM; DICOPPER NITRENES; AZIRIDINATION; LIGAND; ACTIVATION; OXYGEN;

D O I：

10.1039/c4cc03754e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The behavior of the Lewis-acid adducts of two copper-nitrene [Cu(NR)](+) complexes in nitrene-transfer and H-atom abstraction reactions have been demonstrated to depend on the nature of the nitrene substituents. Two-state reactivity, in which a singlet ground state and a nearby triplet excited-state both contribute, provides a useful model for interpreting reactivity trends of the two compounds.

引用

收藏

页码：9852 / 9854

页数：3

相关论文

共 30 条

[1] Mechanistic Insights into C-H Amination via Dicopper Nitrenes [J].

Aguila, Mae Joanne B. ;

Badiei, Yosra M. ;

Warren, Timothy H. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (25) :9399-9406

[2] Transient terminal Cu-nitrene intermediates from discrete dicopper nitrenes [J].

Badiei, Yosra M. ;

Krishnaswamy, Ammani ;

Melzer, Marie M. ;

Warren, Timothy H. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (47) :15056-15057

[3] Copper-Nitrene Complexes in Catalytic C-H Amination [J].

Badiei, Yosra M. ;

Dinescu, Adriana ;

Dai, Xiliang ;

Palomino, Robert M. ;

Heinemann, Frank W. ;

Cundari, Thomas R. ;

Warren, Timothy H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (51) :9961-9964

[4] On the Mechanism of Ligand-Assisted, Copper,Catalyzed Benzylic Amination by Chloramine-T [J].

Barman, Dipti N. ;

Liu, Peng ;

Houk, Kendall N. ;

Nicholas, Kenneth M. .

ORGANOMETALLICS, 2010, 29 (15) :3404-3412

[5] Mechanistic studies of copper-catalyzed alkene aziridination [J].

Brandt, P ;

Södergren, MJ ;

Andersson, PG ;

Norrby, PO .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (33) :8013-8020

[6] The mechanism of the (bispidine)copper(II)-catalyzed aziridination of styrene: A combined experimental and theoretical study [J].

Comba, Peter ;

Lang, Carolin ;

de Laorden, Carlos Lopez ;

Muruganantham, Amsaveni ;

Rajaraman, Gopalan ;

Wadepold, Hubert ;

Zajaczkowski, Marta .

CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (17) :5313-5328

[7] The catalytic mechanism of peptidylglycine α-hydroxylating monooxygenase investigated by computer simulation [J].

Crespo, Alejandro ;

Marti, Marcelo A. ;

Roitberg, Adrian E. ;

Amzel, L. Mario ;

Estrin, Dario A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (39) :12817-12828

[8] Bonding and Structure of Copper Nitrenes [J].

Cundari, Thomas R. ;

Dinescu, Adriana ;

Kazi, Abul B. .

INORGANIC CHEMISTRY, 2008, 47 (21) :10067-10072

[9] Catalytic tuning of a phosphinoethane ligand for enhanced C-H activation [J].

Cundari, Thomas R. ;

Jimenez-Halla, J. Oscar C. ;

Morello, Glenn R. ;

Vaddadi, Sridhar .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (39) :13051-13058

[10] A Computational Study of Metal-Mediated Decomposition of Nitrene Transfer Reagents [J].

Cundari, Thomas R. ;

Morello, Glenn R. .

JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (15) :5711-5714