Well-Defined Copper(I) Amido Complex and Aryl Iodides Reacting to Form Aryl Amines

被引：20

作者：

Delp, Samuel A. ^{[2
]}

Goj, Laurel A. ^{[2
]}

Pouy, Mark J. ^{[1
]}

Munro-Leighton, Colleen ^{[2
]}

Lee, John P. ^{[2
]}

Gunnoe, T. Brent ^{[1
]}

Cundari, Thomas R. ^{[3
]}

Petersen, Jeffrey L. ^{[4
]}

机构：

[1] Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA

[2] N Carolina State Univ, Dept Chem, Raleigh, NC 27695 USA

[3] Univ N Texas, Dept Chem, Denton, TX 76203 USA

[4] W Virginia Univ, C Eugene Bennett Dept Chem, Morgantown, WV 26506 USA

来源：

ORGANOMETALLICS | 2011年 / 30卷 / 01期

基金：

美国国家科学基金会;

关键词：

NITROGEN BOND FORMATION; COUPLING REACTIONS; LIGANDS; CATALYSTS; ANILIDO; SYSTEMS; ACTIVATION; MECHANISMS; AMIDATION; AMINATION;

D O I：

10.1021/om101084e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The Cu-I complex (IPr)Cu(NHPh){IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene} reacts with aryl iodides to form diaryl amine products and (IPr)Cu(I), which was confirmed by independent synthesis and characterization. For the reaction with iodobenzene, the products are diphenylamine and aniline. Protection of the hydrogen para to the iodo functionality with ortho-methyl groups results in quantitative conversion to diaryl amine. Combined computational and experimental studies suggest that C-N bond formation most likely occurs via an oxidative addition/reductive elimination sequence.

引用

页码：55 / 57

页数：3

共 33 条

[1] The copper-catalyzed N-arylation of indoles [J].

Antilla, JC ;

Klapars, A ;

Buchwald, SL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (39) :11684-11688

[2] Copper in cross-coupling reactions - The post-Ullmann chemistry [J].

Beletskaya, IP ;

Cheprakov, AV .

COORDINATION CHEMISTRY REVIEWS, 2004, 248 (21-24) :2337-2364

[3] Synthesis, solid-state crystal structure, and reactivity of a monomeric copper(I) anilido complex [J].

Blue, ED ;

Davis, A ;

Conner, D ;

Gunnoe, TB ;

Boyle, PD ;

White, PS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (31) :9435-9441

[4] Copper(I) diphosphine catalysts for C-N bond formation: Synthesis, structure, and ligand effects [J].

Daly, Stephen ;

Haddow, Mairi F. ;

Orpen, A. Guy ;

Rolls, Giles T. A. ;

Wass, Duncan F. ;

Wingad, Richard L. .

ORGANOMETALLICS, 2008, 27 (13) :3196-3202

[5] Copper(III) and vanadium(IV)-Oxo corrolazines [J].

Fox, JP ;

Ramdhanie, B ;

Zareba, AA ;

Czernuszewicz, RS ;

Goldberg, DP .

INORGANIC CHEMISTRY, 2004, 43 (21) :6600-6608

[6] Enthalpy of Formation of the Cyclohexadienyl Radical and the C-H Bond Enthalpy of 1,4-Cyclohexadiene: An Experimental and Computational Re-Evaluation [J].

Gao, Yide ;

DeYonker, Nathan J. ;

Garrett, E. Chauncey, III ;

Wilson, Angela K. ;

Cundari, Thomas R. ;

Marshall, Paul .

JOURNAL OF PHYSICAL CHEMISTRY A, 2009, 113 (25) :6955-6963

[7] Cu(I)-Amido Complexes in the Ullmann Reaction: Reactions of Cu(I)-Amido Complexes with lodoarenes with and without Autocatalysis by Cul [J].

Giri, Ramesh ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (45) :15860-15863

[8] Cleavage of X-H bonds (X = N, O, or C) by copper(I) alkyl complexes to form monomeric two-coordinate copper(I) systems [J].

Goj, LA ;

Blue, ED ;

Munro-Leighton, C ;

Gunnoe, TB ;

Petersen, JL .

INORGANIC CHEMISTRY, 2005, 44 (24) :8647-8649

[9] Chemistry surrounding monomeric copper(I) methyl, phenyl, anilido, ethoxide, and phenoxide complexes supported by N-heterocyclic carbene ligands:: Reactivity consistent with both early and late transition metal systems [J].

Goj, Laurel A. ;

Blue, Elizabeth D. ;

Delp, Samuel A. ;

Gunnoe, T. Brent ;

Cundari, Thomas R. ;

Pierpont, Aaron W. ;

Petersen, Jeffrey L. ;

Boyle, Paul D. .

INORGANIC CHEMISTRY, 2006, 45 (22) :9032-9045

[10] Formation of aryl-nitrogen bonds using a soluble copper(I) catalyst [J].

Gujadhur, R ;

Venkataraman, D ;

Kintigh, JT .

TETRAHEDRON LETTERS, 2001, 42 (29) :4791-4793

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