Palladium-catalyzed Arylation Reaction Research Articles

Rapid Synthesis of the N‐Methylwelwitindolinone Skeleton.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Rapid Synthesis of theN-Methylwelwitindolinone Skeleton

An efficient, convergent synthesis of the core bicyclo[4.3.1]decane ring system of welwitindolinones is described. Key steps in the synthesis include an intramolecular palladium-catalyzed enolate arylation reaction to create the desired bicyclic skeleton and a Curtius rearrangement to install the bridgehead isocyanate unit. [reaction: see text]

Synthesis of 5,5′-diarylated 2,2′-bithiophenes via palladium-catalyzed arylation reactions

2,2′-Bithiophene and 3,3′-dicyano-2,2′-bithiophenes are diarylated directly with aryl bromides at the 5- and 5′-positions accompanied by C–H bond cleavage in the presence of Pd(OAc) 2 and a bulky phosphine ligand using Cs 2CO 3 as base. In the reaction using (2,2′-bithiophen-5-yl)diphenylmethanol as the substrate, monoarylation at the 5-position via C–C bond cleavage occurs selectively to give 5-aryl-2,2′-bithiophenes and the subsequent arylation with a different aryl bromide affords the corresponding unsymmetrically 5,5′-diarylated products.

Heck‐Type Arylation of 2‐Cycloalken‐1‐ones with Arylpalladium Intermediates Formed by Decarboxylative Palladation and by Aryl Iodide Insertion.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Heck-type arylation of 2-cycloalken-1-ones with arylpalladium intermediates formed by decarboxylative palladation and by aryl iodide insertion.

[reaction: see text] A palladium-catalyzed decarboxylative arylation reaction was shown to produce Heck-type coupling products using a number of different arene carboxylic acid and 2-cycloalken-1-one substrates. The more conventional Heck coupling of an aryl iodide and a 2-cycloalken-1-one reactant was also briefly explored for comparison, where it was found that phosphine-free (Jeffery) conditions afforded the highest yield of product.

Palladium catalyzed arylation reactions of meta photocycloadducts.

We describe the first application of a Heck arylation reaction being performed on a meta photocycloadduct. The resulting arylation/fragmentation process leads to the formation of a bridged bicyclic ketone and constitutes a dramatic increase in molecular complexity after just two synthetic operations.

Variation of Xanthene‐Based Bidentate Ligands in the Palladium‐Catalyzed Arylation of Ureas.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Variation of xanthene-based bidentate ligands in the palladium-catalyzed arylation of ureas

A series of xanthene-based bidentate ligands containing various substituents on diphenylphosphino groups were synthesized and tested in the palladium-catalyzed arylation reaction of urea with unactivated aryl bromides. It was found that both steric and electronic properties of the ligands have a pronounced effect on the yields and ratios of the products. Arylation of urea and phenylurea with unactivated aryl bromides in the presence of Pd 2dba 3·CHCl 3/3,5-(CF 3) 2Xantphos and Cs 2CO 3 as base in dioxane at 100°C gave the corresponding N, N′-diarylureas in 62–98% yields.

Intramolecular C−H Activation by Alkylpalladium(II) Complexes: Insights into the Mechanism of the Palladium-Catalyzed Arylation Reaction

A simple and straightforward method for the synthesis of alkylpalladium complexes such as 1 based on the transmetalation of asymmetrical tetraorganostannanes with PdII complexes is described. The procedure allows for the synthesis of substituted palladacycles as model compounds for the palladium-catalyzed intramolecular arylation reaction.

Intramolecular C-H activation by alkylpalladium(II) complexes: insights into the mechanism of the palladium-catalyzed arylation reaction.

The cyclization of [ArOCH2PdL2Cl] complexes proceeds at room temperature in CH3CN in the presence of base, such as KOPh or carbonate, to form palladacycles. The effect of substituents on the aryl moiety (p-MeO > H >p-NO2) is as expected for an electrophilic aromatic substitution by electrophilic Pd(II). The absence of isotopic effect is also consistent with this proposal. Cyclopalladation proceeds with bidentate ligands (dppf, COD and phen); although the C-H activation reactions are slower in these cases. The starting [ArOCH2Pd(PPh3)2Cl] and [ArOCH2Pd(PPh3)Cl]2 complexes were prepared by transmetalation of organostannanes [(ArOCH2)4Sn] with [Pd(PPh3)2Cl2] or [Pd(PPh3)Cl2]2, respectively. Cleavage of palladacycles with HCl also gave [ArOCH2PdL2Cl] complexes.

Palladium-Catalyzed Cross-Coupling Reactions of Organocopper Derivatives of Methylphosphonic Esters and Amides with Aryl and Hetaryl Iodides

Copper derivatives of methylphosphonic amides are sufficiently stable thermally and can be used in palladium-catalyzed arylation reactions, resulting in synthesis of previously unknown aryl- and hetarylmethylphosphonic tetramethyldiamides in high yields.

PALLADIUM-CATALYZED COUPLING REACTION OF VINYL EPOXIDES, DIOL ACETONIDES, AND DIOL CARBONATES WITH ORGANOBISMUTH COMPOUNDS

The palladium-catalyzed arylation reaction of vinyl epoxides with organobismuth compounds afforded the aryl-substituted (E)-allylic alcohols via ring opening of epoxides. Alternatively, the palladium-catalyzed reaction of diol acetonides and carbonates with bismuth derivatives afforded the aryl-substituted diol acetonides and carbonates without ring opening.

Imposing curvature on a polyarene by intramolecular palladium-catalyzed arylation reactions: A simple synthesis of Dibenzo

Palladium catalysis has been found to offer an effective solution-phase alternative to gas-phase flash vacuum pyrolysis as a method for converting the planar ring system of 7, 10-di(2-bromophenyl)fluoranthene (4) to that of the C(28)H(14) bowl-shaped fullerene fragment dibenzo[a,g]corannulene (5).

Novel synthetic strategy of carbolines via palladium-catalyzed amination and arylation reaction

Four parent carbolines and the corresponding 5- or 9-methylsulfonyl derivatives were synthesized by the palladium-catalyzed intramolecular arylation reaction of ortho-bromo-substituted anilinopyridines which were prepared by the palladium-catalyzed amination reaction of iodobenzenes with aminopyridines. Carbazole and its 9-methylsulfonyl derivative were also synthesized by the same method.

Synthesis of Spiro Polycyclic Aromatic Hydrocarbons by Intramolecular Palladium-Catalyzed Arylation

The palladium-catalyzed intramolecular arylation reaction has been applied to the synthesis of the spiro polycyclic aromatic hydrocarbons and planar polycyclic aromatic hydrocarbons by formation of a six-membered ring. The reaction proceeds more readily with aryl bromides substituted with electron-withdrawing groups by using palladium acetate in N,N-dimethylformamide as the solvent. For the less reactive p-methoxyaryl derivatives the use of LiI as an additive was shown to give the best results. The results obtained in the cyclization of nitro derivatives 21 and 23 suggest that the second step of the cyclization reaction is not an electrophilic substitution reaction.

Synthesis of High-Purity o- and p-Vinyltoluenes by the Heck Palladium-Catalyzed Arylation Reaction

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis of High-Purity o- and p-Vinyltoluenes by the Heck Palladium-Catalyzed Arylation ReactionRobert A. DeVries and Abel MendozaCite this: Organometallics 1994, 13, 6, 2405–2411Publication Date (Print):June 1, 1994Publication History Published online1 May 2002Published inissue 1 June 1994https://doi.org/10.1021/om00018a037RIGHTS & PERMISSIONSArticle Views227Altmetric-Citations34LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (717 KB) Get e-Alerts Get e-Alerts

Synthesis of new 2-arylthieno[3,2-b]thiophenes

2-Arylthieno[3,2-b]thiophenes 1 have been synthesized by palladium catalysed arylation reactions of thieno[3,2-b]thiophene 2 and intramolecular cyclisations of 2,3-substituted thiophenes 7. A comparative study of the different methods is presented.

Chelation-controlled, palladium-catalyzed arylation of enol ethers with aryl triflates. Ligand control of selection for α-or β-arylation of [2-(dimethylamino)ethoxy]ethene.

Palladium-catalyzed arylation reactions of [2-(Dimethylamino)ethoxy]ethene ( 1) with a series of aryl triflates were performed under a variety of reaction conditions. In particular, the influence of phosphine ligands and halide additives on regioselectivity were studied. It was found that the chelation-controlled arylation of 1 affords an expedient route for the conversion of phenols into arylacetaldehydes. Alternatively, the same starting materials could be used to synthesize acetophenones by reversing the regioselectivity with bidentate phosphine ligands.

Regiochemistry of palladium-catalyzed arylation reactions of enol ethers. Electronic control of selection for .alpha.- or .beta.-arylation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRegiochemistry of palladium-catalyzed arylation reactions of enol ethers. Electronic control of selection for .alpha.- or .beta.-arylationCarl Magnus Andersson, Anders Hallberg, and G. Doyle Daves Jr.Cite this: J. Org. Chem. 1987, 52, 16, 3529–3536Publication Date (Print):August 1, 1987Publication History Published online1 May 2002Published inissue 1 August 1987https://doi.org/10.1021/jo00392a007RIGHTS & PERMISSIONSArticle Views1411Altmetric-Citations86LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts