Direct arylation of arene C-H bonds by cooperative action of NHCarbene-Ruthenium(II) catalyst and carbonate via proton abstraction mechanism

被引：342

作者：

Ozdemir, Ismail ^{[3
,4
]}

Demir, Serpil ^{[3
,4
]}

Cetinkaya, Bekir ^{[3
,4
]}

Gourlaouen, Christophe ^{[1
,2
]}

Maseras, Feliu ^{[1
,2
]}

Bruneau, Christian ^{[5
]}

Dixneuf, Pierre H. ^{[5
]}

机构：

[1] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain

[2] Univ Autonoma Barcelona, Dept Quim, Bellaterra 08193, Catalonia, Spain

[3] Inonu Univ, Fac Sci & Arts, Malatya, Turkey

[4] Univ Ege, Fac Sci, Izmir, Turkey

[5] Univ Rennes 1, Inst Sci Chim, F-35042 Rennes, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 04期

关键词：

D O I：

10.1021/ja710276x

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Direct functionalization of sp(2) C-H bonds via ortho diarylation of 2-pyridyl benzene with arylbromides was achieved using ruthenium(II) catalysts containing a RuCl2(NHC) unit and generated from [RuCl2(arene)](2) and two types of NHC precursors, pyrimidinium and benzimidazolium salts, in the presence of Cs2CO3. DFT calculations from RuCl2(NHC)(2-pyridylbenzene) show that a proton abstraction mechanism, on cooperative actions of both the coordinated base and the Ru(II) center, is favoured via a 13.7 kcal mol(-1) exothermic process affording an orthometalated intermediate with a 2.009 angstrom Ru-C bond.

引用

页码：1156 / +

页数：3

共 46 条

[1] Catalytic arylation reactions by C-H bond activation with aryl tosylates
Ackermann, L
Althammer, A
Born, R
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (16) : 2619 - 2622
[2] Phosphine oxides as preligands in ruthenium-catalyzed arylations via C-H bond functionalization using aryl chlorides
Ackermann, L
[J]. ORGANIC LETTERS, 2005, 7 (14) : 3123 - 3125
[3] [RuCl3(H2O)n]-catalyzed direct arylations with bromides as electrophiles
Ackermann, Lutz
Althammer, Andreas
Born, Robert
[J]. SYNLETT, 2007, (18) : 2833 - 2836
[4] Ruthenium(IV) alkylidenes as precatalysts for direct arylations of Alkenes with aryl chlorides and an application to sequential catalysis
Ackermann, Lutz
Born, Robert
Alvarez-Bercedo, Paula
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (33) : 6364 - 6367
[5] Air- and moisture-stable secondary phosphine oxides as preligands in catalysis
Ackermann, Lutz
[J]. SYNTHESIS-STUTTGART, 2006, 10 (10): : 1557 - 1571
[6] Aryl-aryl bond formation by transition-metal-catalyzed direct arylation
Alberico, Dino
Scott, Mark E.
Lautens, Mark
[J]. CHEMICAL REVIEWS, 2007, 107 (01) : 174 - 238
[7] Catalytic intermolecular ortho-arylation of phenols
Bedford, RB
Limmert, ME
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (22) : 8669 - 8682
[8] Catalytic direct arylation with aryl chlorides, bromides, and iodides: Intramolecular studies leading to new intermolecular reactions
Campeau, LC
Parisien, M
Jean, A
Fagnou, K
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (02) : 581 - 590
[9] η6-mesityl,η1-imidazolinylidene-carbene-ruthenium(II) complexes:: Catalytic activity of their allenylidene derivatives in alkene metathesis and cycloisomerisation reactions
Çetinkaya, B
Demir, S
Özdemir, I
Toupet, L
Sémeril, D
Bruneau, C
Dixneuf, PH
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (10) : 2323 - 2330
[10] Chatani N, 2007, TOP ORGANOMETAL CHEM, V24, P1, DOI 10.1007/978-3-540-75809-9

← 1 2 3 4 5 →