Mechanistic Duality in Palladium-Catalyzed Cross-Coupling Reactions of Aryldimethylsilanolates. Intermediacy of an 8-Si-4 Arylpalladium(II) Silanolate

被引：30

作者：

Denmark, Scott E. ^{[1
]}

Smith, Russell C. ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Roger Adams Lab, Urbana, IL 61801 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 04期

基金：

美国国家卫生研究院;

关键词：

C BOND ACTIVATION; KINETIC-ANALYSIS; COMPLEXES; ARYL; TRANSMETALATION; ELIMINATION; STEREOCHEMISTRY; ALKYLBORANES; BORON;

D O I：

10.1021/ja907049y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of palladium-catalyzed cross-coupling reactions of potassium (4-methoxyphenyl)dimethyl silanolate has been investigated. Under catalysis by (t-Bu(3)P)(2)Pd, the Coupling with 1-bromo-4-fluorobenzene displays the following rate equation: rate = k(obs)[R(3)SiOK](0)[ArylBr](0), with k(obs) = k[(t-Bu(3)P)(2)Pd](0.98). An independent study of the individual steps of the catalytic cycle has revealed a dual mechanistic pathway. The transmetalation can occur by a thermal process via an 8-Si-4 intermediate without the need for anionic activation. Additionally, arylsilanolates can serve as activators for transmetalation via a hypervalent 10-Si-5 siliconate intermediate.

引用

页码：1243 / +

页数：5

共 25 条

[1] Effect of Ligand Steric Properties and Halide Identity on the Mechanism for Oxidative Addition of Haloarenes to Trialkylphosphine Pd(0) Complexes [J].

Barrios-Landeros, Fabiola ;

Carrow, Brad P. ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (23) :8141-8154

[2] Computational study of the transmetalation process in the Suzuki-Miyaura cross-coupling of aryls [J].

Braga, Ataualpa A. C. ;

Morgon, Nelson H. ;

Ujaque, Gregori ;

Lledos, Agusti ;

Maseras, Feliu .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2006, 691 (21) :4459-4466

[3] A DFT study of the full catalytic cycle of the Suzuki-Miyaura cross-coupling on a model system [J].

Braga, Ataualpa A. C. ;

Ujaque, Gregori ;

Maseras, Feliu .

ORGANOMETALLICS, 2006, 25 (15) :3647-3658

[4] The first general method for palladium-catalyzed Negishi cross-coupling of aryl and vinyl chlorides:: Use of commercially available Pd(P(t-BU)3)2 as a catalyst [J].

Dai, CY ;

Fu, GC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (12) :2719-2724

[5]

de Meijere A., 2004, MetalCatalyzed CrossCoupling Reactions, V1

[6] Palladium-Catalyzed Cross-Coupling Reactions of Organosilanols and Their Salts: Practical Alternatives to Boron- and Tin-Based Methods [J].

Denmark, Scott E. ;

Regen, Christopher S. .

ACCOUNTS OF CHEMICAL RESEARCH, 2008, 41 (11) :1486-1499

[7] Cross-Coupling Reactions of Aromatic and Heteroaromatic Silanolates with Aromatic and Heteroaromatic Halides [J].

Denmark, Scott E. ;

Smith, Russell C. ;

Chang, Wen-Tau T. ;

Muhuhi, Joseck M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (08) :3104-3118

[8] Palladium-catalyzed cross-coupling reactions of substituted aryl(dimethyl)silanols [J].

Denmark, SE ;

Ober, MH .

ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (13-15) :1703-1714

[9] Fluoride-promoted cross-coupling reactions of alkenylsilanols. Elucidation of the mechanism through spectroscopic and kinetic analysis [J].

Denmark, SE ;

Sweis, RF ;

Wehrli, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (15) :4865-4875

[10] Cross-coupling reactions of alkenylsilanolates. Investigation of the mechanism and identification of key intermediates through kinetic analysis [J].

Denmark, SE ;

Sweis, RF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (15) :4876-4882

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