Pyrene-Based Mono- and Di-N-Heterocyclic Carbene Ligand Complexes of Ruthenium for the Preparation of Mixed Arylated/Alkylated Arylpyridines

被引：42

作者：

Gonell, Sergio ^{[1
]}

Peris, Eduardo ^{[1
]}

机构：

[1] Univ Jaume I Avda, Dept Quim Inorgan & Organ, Castellon de La Plana 12071, Spain

来源：

ACS CATALYSIS | 2014年 / 4卷 / 08期

关键词：

ruthenium; N-heterocyclic carbene; Janus; tandem; arylation of arylpyridines; hydroarylation of alkenes; H BOND ACTIVATION; DIRECT ORTHO ARYLATION; ELECTRONIC COMMUNICATION; TANDEM CATALYSIS; ARYL CHLORIDES; METAL-METAL; FUNCTIONALIZATIONS; ALKENYLATION; CENTERS; ALKENES;

D O I：

10.1021/cs500735u

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：

By using two pyrene-based mono- and di-N-heterocyclic carbene ligands, two ruthenium complexes (one monometallic and the other dimetallic) have been obtained and fully characterized. The molecular structure of the dimetallic complex has been determined by means of X-ray diffraction studies. The electrochemical studies reveal that the metal-metal communication in the dimetallic complex is weak. The catalytic activity of both complexes has been tested in the arylation of arylpyridines with aryl halides and in the hydroarylation of alkenes, where they showed similar activity. The sequential combination of these two catalytic processes (hydroarylation of alkenes followed by arylation of the resulting alkyl-substituted arylpyridine) allowed the preparation of mixed arylated/alkylated arylpyridines. In this tandem process, the dimetallic complex afforded activity higher than that of the monometallic complex. The activity was compared to that shown by the [RuCl2(p-cymene)](2) complex. This reaction constitutes an efficient method for reaching unsymmetrically substituted arylpyridines.

引用

页码：2811 / 2817

页数：7

共 40 条

[1] Assisted ruthenium-catalyzed C-H bond activation: Carboxylic acids as cocatalysts for generally applicable direct arylations in apolar solvents [J].

Ackermann, Lutz ;

Vicente, Ruben ;

Althammer, Andreas .

ORGANIC LETTERS, 2008, 10 (11) :2299-2302

[2] Ruthenium(IV) alkylidenes as precatalysts for direct arylations of Alkenes with aryl chlorides and an application to sequential catalysis [J].

Ackermann, Lutz ;

Born, Robert ;

Alvarez-Bercedo, Paula .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (33) :6364-6367

[3] Carboxylate-Assisted Transition-Metal-Catalyzed C-H Bond Functionalizations: Mechanism and Scope [J].

Ackermann, Lutz .

CHEMICAL REVIEWS, 2011, 111 (03) :1315-1345

[4] Ruthenium-Catalyzed Direct Arylations Through C-H Bond Cleavages [J].

Ackermann, Lutz ;

Vicente, Ruben .

C-H ACTIVATION, 2010, 292 :211-229

[5] Metal-catalyzed direct alkylations of (hetero)arenes via C-H bond cleavages with unactivated alkyl halides [J].

Ackermann, Lutz .

CHEMICAL COMMUNICATIONS, 2010, 46 (27) :4866-4877

[6] Transition-Metal-Catalyzed Direct Arylation of (Hetero)Arenes by C-H Bond Cleavage [J].

Ackermann, Lutz ;

Vicente, Ruben ;

Kapdi, Anant R. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (52) :9792-9826

[7] Regioselective Ruthenium-Catalyzed Direct Benzylations of Arenes through C-H Bond Cleavages [J].

Ackermann, Lutz ;

Novak, Petr .

ORGANIC LETTERS, 2009, 11 (21) :4966-4969

[8] Two birds with one metallic stone: Single-pot catalysis of fundamentally different transformations [J].

Ajamian, A ;

Gleason, JL .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (29) :3754-3760

[9] Grubbs' Ruthenium-Carbenes Beyond the Metathesis Reaction: Less Conventional Non-Metathetic Utility [J].

Alcaide, Benito ;

Almendros, Pedro ;

Luna, Amparo .

CHEMICAL REVIEWS, 2009, 109 (08) :3817-3858

[10] Ruthenium(II)-catalyzed selective monoarylation in water and sequential functionalisations of C-H bonds [J].

Arockiam, Percia B. ;

Fischmeister, Cedric ;

Bruneau, Christian ;

Dixneuf, Pierre H. .

GREEN CHEMISTRY, 2013, 15 (01) :67-71

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