Palladium-catalyzed Hiyama Cross-coupling Reaction Research Articles

Stereoselective Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Tetrasubstituted gem-Difluoroalkenes.

We herein describe a diastereoselective Pd(0)-catalyzed Hiyama cross-coupling reaction of gem-difluoroalkenes. The use of organosilicon reagents in this reaction is advantageous over other organometallic reagents by allowing the introduction of a wide range of functional groups, including challenging alkyl groups. Also conveniently, the additive TBAF was not required for (hetero)aryl-substituted difluoroalkenes.

Palladium-Catalyzed Hiyama Cross-Couplings of Arylsilanes with 3-Iodoazetidine: Synthesis of 3-Arylazetidines.

The first palladium-catalyzed Hiyama cross-coupling reactions of arylsilanes with 3-iodoazetidine were described. The protocol provides a convenient access to a variety of useful 3-arylazetidines which are of great interest in pharmaceutical laboratories in moderate to good yields (30%-88%). In addition, this strategy has the advantage of easy operation and mild reaction conditions.

ChemInform Abstract: A General Palladium‐Catalyzed Hiyama Cross‐Coupling Reaction of Aryl and Heteroaryl Chlorides.

AbstractThe reaction can be run with low catalyst loadings (0.05‐1 mol%).

A General Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl and Heteroaryl Chlorides.

A general palladium-catalyzed Hiyama cross-coupling reaction of aryl and heteroaryl chlorides with aryl and heteroaryl trialkoxysilanes by a Pd(OAc)2 /L2 catalytic system is presented. A newly developed water addition protocol can dramatically improve the product yields. The conjugation of the Pd/L2 system and the water addition protocol can efficiently catalyze a broad range of electron-rich, -neutral, -deficient, and sterically hindered aryl chlorides and heteroaryl chlorides with excellent yields within three hours and the catalyst loading can be down to 0.05 mol % Pd for the first time. Hiyama coupling of heteroaryl chlorides with heteroaryl silanes is also reported for the first time. The reaction can be easily scaled up 200 times (100 mmol) without any degasification and purification of reactants; this facilitates the practical application in routine synthesis.

1-(Triethoxysilyl)buta-1,3-dienes-New Building Blocks for Stereoselective Synthesis of Unsymmetrical (E,E)-1,4-Disubstituted 1,3-dienes.

A convenient methodology for the highly stereoselective synthesis of unsymmetrical (1E,3E)-1,4-disubstituted 1,3-dienes based on palladium-catalyzed Hiyama cross-coupling reaction of 1-(triethoxysilyl)-substituted buta-1,3-dienes with aryl iodides is reported.

Palladium-catalyzed Hiyama coupling reaction of arylsulfonyl hydrazides under oxygen.

Palladium-catalyzed Hiyama cross-coupling reactions of various arylsulfonyl hydrazides with a wide variety of aryl silanes have been achieved in good to excellent yields under simple conditions. The newly developed catalytic system does not require the use of expensive silver- or copper-based stoichiometric oxidants and can be accelerated by the addition of TBAT under an atmosphere of oxygen. The reported Hiyama-type coupling reactions are tolerant to common functional groups, making these transformations attractive alternatives to the traditional cross-coupling approaches.

MIDA as a simple and highly efficient ligand for palladium-catalyzed Hiyama cross-coupling of aryl halides.

N-Methyliminodiacetic acid (MIDA) as a simple, air stable and water-soluble ligand has been used in the palladium-catalyzed Hiyama cross-coupling reaction of trimethoxyphenylsilane with aryl halides. The yield of the corresponding Hiyama coupling products is high up to around 90% in water and isopropanol under an ambient atmosphere in the presence of KOH and NaF.

Palladium-Catalyzed Hiyama Cross-Coupling of Aryltrifluorosilanes with Aryl and Heteroaryl Chlorides

An efficient, palladium-catalyzed Hiyama cross-coupling reaction of aryltrifluorosilanes with aryl chlorides has been developed. A wide variety of functionalized biaryl derivatives were isolated in good to excellent yields. The scope of this reaction has also been extended to heteroaryl chlorides, affording the corresponding heterobiaryl compounds in high yields.

Silica-Supported Palladium-Catalyzed Hiyama Cross-Coupling Reactions Using Continuous Flow System

reactions have been used in the continuous flow reaction with a variety of immobilized palladium catalysts.To the best of our knowledge, the Hiyama cross-coupling reaction has never been used in a continuous micro-flow re-action, despite the many advantages of the silyl reagent such as its stability in air stable, nontoxicity and easy availability.

Application of Cyclic Thiourea as an Efficient Ligand in Palladium-Catalyzed Hiyama Cross-Coupling Reactions

Cyclic thiourea has been first utilized as an efficient ligand in palladium-catalyzed Hiyama cross-coupling reactions. In the presence of palladium(II) acetate, N, N′-bis(2,5-di- TERT-butylphenyl)- N, N′-ethylenethiourea, tetrabutylammonium fluoride, and dioxane, aryl halides (X = I, Br, Cl) underwent smooth cross coupling with trimethoxy(phenyl)silane to afford the corresponding biaryl products in moderate to excellent yields. Furthermore, the thiourea can be recovered by column chromatography and reused with negligible loss in catalytic activity.

Improved Procedure for Palladium‐Catalyzed Hiyama Cross‐Coupling Reaction of Aryl Halides with Aryltrimethoxysilanes under Solvent‐Free Conditions.

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Improved Procedure for Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl Halides with Aryltrimethoxysilanes under Solvent-Free Conditions

An improved palladium-catalyzed Hiyama cross-coupling reaction is reported. In the presence of PdCl 2 (MeCN) 2 , P(o-tol) 3 and TBAF, a number of ArX (X = I, Br, Cl) were coupled with ArSi(OMe) 3 efficiently to afford the desired cross-coupled products in moderate to excellent yields. It is noteworthy that this protocol is conducted under relatively low Pd loadings and solvent-free conditions.