Palladium‐catalyzed reductive homocoupling of aryl sulfonates via cleavage of C─O bond at room temperature

Palladium‐catalyzed reductive homocoupling of aryl sulfonates has been successfully achieved under mild conditions. This transformation is a new method for the homocoupling reaction of aryl sulfonates at room temperature via the cleavage of C─O bonds, thus providing an alternative synthesis of symmetric biaryls. The reported reductive homocoupling reaction is tolerant of many common functional groups regardless of electron‐donating or electron‐withdrawing nature, making this newly developed transformation important for complementing Ullmann coupling. Experimental Section. Typical procedure for the products.     

Effective heterogeneous palladium catalysis of the reactions of organoboron compounds with aryl halides

Reactions of [Ph₄B]Na and ArB(OH)₂ with aryl halides are effectively catalyzed by heterogeneous palladium catalysts (PdCl₂C, Pd(0)/C, and palladium black) to give cross-coupling products in high yields. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1399–1401, July, 1997.     

Benzimidazolin‐2‐ylidene–palladium‐catalysed coupling reactions of aryl halides

The in situ prepared three‐component system Pd(OAc)₂–1,3‐dialkylbenzimidazolium chlorides ( 2a – f ) and Cs₂CO₃ catalyses, quantitatively, the Suzuki cross‐coupling of deactivated aryl chlorides and Heck coupling reactions of aryl bromide and iodide substrates. The 1,3‐dialkylbenzimidazolium salts ( 2a – f ) were characterized by conventional spectroscopic methods and elemental analysis. Copyright © 2005 John Wiley & Sons, Ltd.     

Oxidative homocoupling of arylboronic acids catalyzed by a 4‐aminoantipyrine–Pd(II)complex

A one‐step synthesis of symmetric biaryls is reported under very mild conditions via the homocoupling reaction of substituted arylboronic acids using an air‐ and moisture‐stable 4‐aminoantipyrine–Pd(II) complex as catalyst. The reaction is conducted at a low catalyst loading of 0.1 mol% at room temperature in methanol in the presence of K₂CO₃ as the base and KMnO₄ as the oxidant. The catalytic methodology is shown to be compatible with diverse functional groups and affords the desired biphenyls in good to excellent yields. Copyright © 2015 John Wiley & Sons, Ltd.     

Pd/C-catalyzed room-temperature hydrodehalogenation of aryl halides with hydrazine hydrochloride

Treatment of aryl and heteroaryl halides with catalytic amounts of Pd/C in the presence of hydrazine hydrochloride in basic medium (sodium hydroxide or sodium t-butylate) at room temperature leads to the corresponding hydrodehalogenation products with high selectivity. Aryl iodides, bromides, chlorides and fluorides can be reduced using this reagent combination. The reduction is compatible with various electron-donating or electron-withdrawing groups.     

Mild and efficient Pd(PtBu3)2‐catalyzed aminocarbonylation of aryl halides to aryl amides with high selectivity

This work describes a mild and efficient approach for the synthesis of aryl amides via catalytic aminocarbonylation of aryl halides with alicyclic amines using a Pd(P^t Bu₃)₂/NH₄Cl catalyst system. Under mild reaction temperature of 60°C and balloon pressure of CO, 5 mol% Pd(P^t Bu₃)₂ with a cheap NH₄Cl promoter is sufficient for high yields of aryl amides. The influence of reaction parameters such as reaction temperature, ligand type and promoter on catalytic activity was investigated. This work also discusses the catalytic intermediates in detail, and provides a plausible mechanism based on an acid chloride intermediate.     

Homocoupling of aryl halides promoted by an NiCl2/bpy/Mg system in DMF

Homocoupling of aryl halides (2 ArX → Ar―Ar) promoted by NiCl₂/2,2′‐bipyridine (bpy)/Mg mixtures in DMF has been studied. Mixtures of NiCl₂, bpy and Mg in DMF promoted homocoupling of aryl halides such as phenyl bromide and p‐tolyl bromide to give the coupling products in good (e.g. approximately 60–75%) yields, and the homocoupling products were easily isolated from the reaction mixtures. Application of this homocoupling to dibromo‐aromatic compounds (Br–arylene–Br: 2,5‐dibromopyridine, 2,7‐dibromo‐9.9‐dioctylfluorene and 2,7‐dibromo‐9,10‐dioctyl‐9,10‐dihydrophenanthrene) gave the corresponding π‐conjugated polymers, –(arylene)_n–, in good yields. Organometallic processes for the homocoupling are discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

The first heterogeneous Sonogashira coupling reaction of aryl halides with terminal alkynes catalyzed by diatomite‐supported palladium(II) salophen complex

We report here our observation that, using appropriate reaction conditions, the Sonogashira reaction can be performed without the need for copper catalyst and solvent. Our approach involves the use of diatomite‐supported palladium(II) salophen complex as a catalyst and triethylamine as a base. The methodology works, to differing extents, for aryl iodides and bromides. This heterogeneous catalyst can be reused at least five times without any decrease in activity. Copyright © 2011 John Wiley & Sons, Ltd.     

Dimer formation in the reaction of aryl halides catalyzed by nickel complexes

The synthesis of diaryls catalyzed by electrochemically generated zero-valent nickel with 2,2-diapyridyl as the ligand was carried out from aryl halides in high yield. Feasibility was demonstrated for synthesizing the catalyst itself by the anodic dissolution of nickel in the presence of 2-bromopyridine in a diaphragmless cell.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1674–1676, July, 1992.     

An improved procedure for the synthesis of arylboronates by palladium‐catalyzed coupling reaction of aryl halides and bis(pinacolato)diboron in polyethylene glycol

A new protocol has been developed for the synthesis of arylboronates by a coupling reaction of aryl halides and bis(pinacolato)diboron using bis(triphenylphosphine)palladium dichloride/sodium acetate/polyethylene glycol 600 [Pd(PPh₃)₂Cl₂/NaOAc/PEG 600] as an efficient catalytic system. Copyright © 2011 John Wiley & Sons, Ltd.     

Palladium‐Catalyzed,tert‐Butyllithium‐Mediated Dimerization of Aryl Halides and Its Application in the Atropselective Total Synthesis of Mastigophorene A

A palladium‐catalyzed direct synthesis of symmetric biaryl compounds from aryl halides in the presence of tBuLi is described. In situ lithium–halogen exchange generates the corresponding aryl lithium reagent, which undergoes a homocoupling reaction with a second molecule of the aryl halide in the presence of the palladium catalyst (1 mol %). The reaction takes place at room temperature, is fast (1 h), and affords the corresponding biaryl compounds in good to excellent yields. The application of the method is demonstrated in an efficient asymmetric total synthesis of mastigophorene A. The chiral biaryl axis is constructed with an atropselectivity of 9:1 owing to catalyst‐induced remote point‐to‐axial chirality transfer.     

Nickel‐catalyzed aminocarbonylation of aryl halides with carbamoylsilanes: efficient synthesis of secondary (primary) aromatic amides

A nickel‐catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source leading to corresponding secondary or primary aromatic amides has been developed, in which the methoxymethyl and benzyl were used as amino protecting group. The protocol tolerates a broad range of aryl halides bearing different functional groups to afford good yields of aryl amides under mild reaction conditions. The types and the relative positions of substituents on the aryl ring make a notable impact on the coupling efficiency. The plausible mechanism of nickel‐catalyzed aminocarbonylation has been suggested.     

Amine‐bridged bis(phenol) ligands for efficient Pd‐catalyzed aqueous C‐C coupling reactions

The influence of ring size ( 5 or 6 ), chain length ( 1 , 2 or 3 ) and bulkiness of N‐aryl substituents in amine‐bridged bis(phenol) ligands ( 1 , 2 , 3 ) on palladium‐catalyzed aqueous C‐C coupling reactions were revealed. The homocoupling of arylboronic acid can be completed in neat water with the aid of a catalytic amount of p‐toluenesulfonyl chloride (TsCl) in a very short time under anaerobic or aerobic conditions. Interestingly, the same catalytic system was efficient for Suzuki–Miyaura reaction in aqueous acetone under aerobic conditions in the absence of TsCl. The crystal structures of ligand 1 and three unsymmetrical fluorine‐substituted biaryl derivatives were also reported. Copyright © 2013 John Wiley & Sons, Ltd.     

CuBr/proline‐catalyzed cross‐coupling of unactivated benzene with aryl halides

Direct C? H arylation of unactivated benzene with aryl halides was achieved using a readily available copper catalyst. The reaction was carried out at 80 °C, using CuBr as catalyst, proline as ligand and t‐BuOK as base. This radical cross‐coupling reaction between unactivated benzene and aryl iodides proceeds via homolytic aromatic substitution and offers an efficient method for the synthesis of various biaryls in good to excellent yields. Copyright © 2015 John Wiley & Sons, Ltd.     

N‐Heterocyclic carbene/phosphite synergistically assisted Pd/C‐catalyzed Suzuki coupling of aryl chlorides

An N‐heterocyclic carbene and phosphite synergistically enhanced Pd/C catalyst system has been developed for Suzuki coupling of aryl chlorides and aryl boronic acids from commercially available Pd/C with sterically demanding N,N′‐bis(2,6‐diisopropylphenyl)imidazolylidene and trimethylphosphite. A remarkable increase in catalytic activity of Pd/C was observed when used along with 1 equiv. N,N′‐bis(2,6‐diisopropylphenyl)imidazolium chloride and 2 equiv. phosphite with respect to palladium in appropriate solvents that were found to play a crucial role in Pd/C‐NHC‐P(OR)₃‐catalyzed Suzuki coupling. A dramatic ortho‐substitution effect of carbonyl and nitrile groups in aryl chlorides was observed and explained by a modified quasi‐heterogeneous catalysis mechanism. The Pd/C catalyst could be easily recovered from reaction mixtures by simple filtration and only low palladium contamination was detected in the biparyl products. A practical process for the synthesis of 4‐biphenylcarbonitrile has therefore been developed using the N‐heterocyclic carbene/phosphite‐assisted Pd/C‐catalyzed Suzuki coupling. Copyright © 2013 John Wiley & Sons, Ltd.     

Hemilabile‐coordinated copper promoted amination of aryl halides with ammonia in aqueous ethylene glycol under atmosphere pressure

Direct amination of aryl iodides and bromides with ammonia under 1 atm pressure has been effected using in situ‐generated hemilabile coordinated copper(I) species from copper(I) halides or copper metal in aqueous ethylene glycol, producing primary aromatic amines in good yields. Ammonia pressure and water were found to accelerate the copper‐mediated reaction while strong chelating ligands showed a suppression effect. A rationale for the copper‐mediated amination of aryl halides with ammonia is given based on a double‐face role of chelating effect. Copyright © 2009 John Wiley & Sons, Ltd.     

Heck reactions of aryl halides with alk‐1‐en‐3‐ol derivatives catalysed by a tetraphosphine–palladium complex

cis,cis,cis‐1,2,3,4‐Tetrakis(diphenylphosphinomethyl)cyclopentane–[PdCl(C₃H₅)]₂ efficiently catalyses the Heck reaction of alk‐1‐en‐3‐ol with a variety of aryl halides. In the presence of hex‐1‐en‐3‐ol or oct‐1‐en‐3‐ol, the β‐arylated carbonyl compounds were selectively obtained. Turnover numbers up to 84 000 can be obtained for this reaction. Linalool and 2‐methylbut‐3‐en‐2‐ol led regio‐ and stereoselectively to the corresponding (E)‐1‐arylalk‐1‐en‐3‐ol derivatives. A minor electronic effect of the substituents of the aryl bromide was observed. Quite similar reaction rates were generally observed in the presence of activated aryl bromides such as bromoacetophenone and deactivated aryl bromides such as bromoanisole, indicating that, with these alkenols and this catalyst, the oxidative addition of aryl bromides to palladium is not the rate‐limiting step. It should be noted that this reaction also proceeds with sterically very congested aryl bromides such as 9‐bromoanthracene or 2,4,6‐triisopropylbromobenzene or with a vinyl bromide. On the other hand, low yields were obtained with aryl chlorides. Copyright © 2006 John Wiley & Sons, Ltd.     

Suzuki–Miyaura coupling reactions of aryl chlorides catalyzed by a new nickel(II) σ‐aryl complex

A new nickel(II) σ‐aryl complex, trans‐chloro(9‐phenanthrenyl)bis(triphenylphosphine)nickel(II), was used as a precatalyst for the Suzuki–Miyaura coupling reactions of aryl chlorides. The catalytic conditions were optimized by investigating the cross‐coupling of p‐chloroanisole with phenylboronic acid. The results show that this complex is efficient for both electron‐rich and electron‐deficient aryl chlorides, though it gives better yields for activated arylboronic acids than deactivated ones. All isolated cross‐coupled biaryl products have been characterized by ¹H and ¹³C NMR, and their spectral data are consistent with those reported. Side products from the coupling of arylboronic acid with the precatalyst complex have also been isolated and characterized, which is helpful for understanding the coupling mechanism. Copyright © 2013 John Wiley & Sons, Ltd.     

Palladium catalyzed reductive homocoupling reactions of aromatic halides in dimethyl sulfoxide (DMSO) solution

Biaryls were obtained in good to excellent yields from the palladium catalyzed reductive homocoupling reactions of various aryl iodides and bromides in dimethyl sulfoxide (DMSO) solution without the need for any additional reducing reagents. Pd(dppf)Cl₂ is the most effective among the screened palladium catalysts for the homocoupling reactions. Fluorides, carbonates, acetates and hydroxides can be used as bases at promoting the palladium catalyzed reductive homocoupling of aryl halides in DMSO solution. X-ray photoelectron spectroscopic (XPS) analysis shows that the oxidative Pd²⁺(dppf) species can be reduced into the Pd⁰(dppf) active species by solvent DMSO molecules to furnish the catalytic cycle, indicating that DMSO plays a dual role as both solvent and reducing reagent. A plausible reaction mechanism has been discussed. Elimination of additional reducing reagents will not only reduce the reaction operation cost, but will also simplify the product separation and purification.     

Efficient construction of C–C bonds from aryl halides/aryl esters with arylboronic acids catalysed by palladium(II) thiourea complexes

A new set of palladium(II) complexes comprising phenyl(thiazolyl)thiourea ligands have been successfully synthesized and characterized with the aid of analytical as well as spectral (IR, UV–visible and NMR) methods. A distorted square‐planar geometry with N^S coordination mode of thiourea ligands in the new palladium complexes was corroborated by single‐crystal X‐ray diffraction methods. Interestingly, the palladium(II) thiourea complexes showed the highest catalytic activity with 0.1 mol% catalyst loading in Suzuki–Miyaura cross‐coupling reactions utilizing a range of aryl bromides/unactivated aryl chlorides with arylboronic acids as coupling partners in aqueous–organic media. Syntheses of diaryl ketones using aryl esters and arylboronic acids as coupling partners were also achieved with low catalyst loading within 20 h. The potential of our catalyst was demonstrated by its wide substrate scope, low catalyst loadings and high isolated yield. Moreover, the influences of key parameters like solvent, base, temperature and catalyst loading were also investigated.