Palladium-Catalyzed One-Pot Synthesis Research Articles

Optimization of Palladium-Catalyzed One-Pot Synthesis of Functionalized Furans for High-Yield Production: A Study of Catalytic and Reaction Parameters

This study investigates the palladium-catalyzed one-pot synthesis of functionalized furans from 1,3-Dicarbonyl compounds and alkenyl bromides, focusing on various catalysts and reaction parameters. Different catalysts, including PdCl₂(CH₃CN)₂, Pd(OAc)₂, and Pd(acac)2 as well as solvents, bases, and oxidants, were systematically evaluated. PdCl₂(CH₃CN)₂ emerged as the most effective catalyst, achieving a remarkable yield of 94%. Optimal reaction conditions were identified as PdCl₂(CH₃CN)₂ in dioxane at 80 °C with K₂CO₃ as the base and CuCl₂ as the oxidant. This study also explored various 1,3-diketones including Cyclohexane-1,3-dione, 5,5-Dimethylcyclohexane-1,3-dione, 2H-Pyran-3,5(4H,6H)-dione, Cyclopentane-1,3-dione, Pentane-2,4-dione, Ethyl 3-oxobutanoate, 1,3-Diphenylpropane-1,3-dione, 1,3-Dip-tolylpropane-1,3-dione, 1,3-Bis(4-chlorophenyl)propane-1,3-dione, and 1,3-Bis(4-bromo- phenyl)propane-1,3-dione, alongside different alkenyl bromides such as allyl bromide, (E)-1-Bromo-3,4-dimethylpent-2-ene, 1-Bromo-3-methylbut-2-ene, 3-Bromocyclohex-1-ene, and (E)-1-Bromohex-2-ene. These variations demonstrated the method’s versatility and the significant impact of substituents on reactivity and reaction yield. These findings highlight the importance of optimizing reaction conditions to maximize efficiency and provide insights into improving catalytic processes for enhanced product yields.

Silver-assisted palladium-catalyzed one-pot synthesis of 3-(hetero)arylmethyl derivatives of imidazo[1,2-a]pyridines

Silver-assisted palladium-catalyzed one-pot synthesis of 3-(hetero)arylmethyl derivatives of imidazo[1,2-a]pyridines

Palladium-catalyzed one-pot synthesis of 2-substituted quinazolin-4(3H)-ones from o-nitrobenzamide and alcohols.

Palladium-catalyzed 2-substituted quinazolin-4(3H)-one formation from readily available o-nitrobenzamides and alcohols using hydrogen transfer is described. Various quinazolin-4(3H)-ones were obtained in good to high yields. The cascade reaction including alcohol oxidation, nitro reduction, condensation, and dehydrogenation occurs without any added reducing or oxidizing agent.

Palladium-catalyzed one-pot cycloaddition reactions of thioureas with 3H-indol-3-ones generatedin situfrom 2-alkynyl arylazides: rapid and efficient access to imidazoloindolines

An efficient palladium-catalyzed one-pot synthesis of imidazoloindolines from 2-alkynyl arylazides under mild reaction conditions has been described.

Palladium-Catalyzed One-Pot Stereospecific Synthesis of 2-Deoxy Aryl C-Glycosides from Glycals and Anilines in the Presence of tert-Butyl Nitrite

The palladium-catalyzed one-pot synthesis of 2,3-deoxy-3-keto aryl C-glycosides is achieved from glycals and anilines in the presence of tert-butyl nitrite and aqueous HBF4 under mild conditions. This one-pot method stereospecifically provides α- and β-aryl glycosides (≥19:1 by NMR) in good yields at room temperature. The configuration at the C-3 position in the glycal determines the anomeric selectivity (i.e., α or β) of the desired products.

Cover Picture: Palladium-Catalyzed One-Pot Synthesis of 5-(1-Arylvinyl)-1H -benzimidazoles: Overcoming the Limitation of Acetamide Partners (Adv. Synth. Catal. 11/2016)

Cover Picture: Palladium-Catalyzed One-Pot Synthesis of 5-(1-Arylvinyl)-1<i>H</i> -benzimidazoles: Overcoming the Limitation of Acetamide Partners (Adv. Synth. Catal. 11/2016)

ChemInform Abstract: Palladium‐Catalyzed Phthalazinone Synthesis Using Paraformaldehyde as Carbon Source.

A palladium-catalyzed one-pot synthesis of phthalazinones from 2-halomethyl benzoates, paraformaldehyde, and aryl hydrazines is described. Various substituted phthalazinones were selectively obtained in good yields using paraformaldehyde as the cheap carbon source (CH).

Palladium-catalyzed one-pot synthesis of diazoles via tert-butyl isocyanide insertion.

An efficient one-pot palladium-catalyzed reaction for the synthesis of diazoles from readily available hydrazides and aryl halide via isocyanide insertion/cyclization sequence has been developed. This methodology efficiently constructs diazoles in good to excellent yields with the advantages of wide functional group tolerance and operational simplicity.

ChemInform Abstract: Palladium‐Catalyzed Tandem Reaction of 2‐Hydroxyarylacetonitriles with Sodium Sulfinates: One‐Pot Synthesis of 2‐Arylbenzofurans.

AbstractThe presented approach is suited to be scaled up.

Palladium-Catalyzed Phthalazinone Synthesis Using Paraformaldehyde as Carbon Source

A palladium-catalyzed one-pot synthesis of phthalazinones from 2-halomethyl benzoates, paraformaldehyde, and aryl hydrazines is described. Various substituted phthalazinones were selectively obtained in good yields using paraformaldehyde as the cheap carbon source (CH).

Palladium-Catalyzed One-Pot Synthesis of Oxazolopyrazines by Heteroannulation

Palladium-Catalyzed One-Pot Synthesis of Oxazolopyrazines by Heteroannulation

Palladium-catalyzed one-pot synthesis of benzo[b][1,6]naphthyridines via Sonogashira coupling and annulation reactions from 2-chloroquinoline-3-carbonitriles

Palladium-catalyzed one-pot synthesis of 1,3-disubstituted benzo[b][1,6]naphthyridines and [1,6]naphthyridines has been described from easily accessible precursors, 2-chloroquinoline-3-carbonitriles and 2-chloropyrido-3-carbonitrile via sequential additions of palladium-catalyst for Sonogashira-coupling and the following annulations in good to excellent yields. A plausible mechanism for annulation is discussed.

One-Pot Synthesis of Substituted Benzo[b]furans from Mono- and Dichlorophenols Using Palladium Catalysts Bearing Dihydroxyterphenylphosphine

A dihydroxyterphenylphosphine bearing cyclohexyl groups on the phosphorus atom (Cy-DHTP) was found to be a powerful ligand for the palladium-catalyzed one-pot synthesis of substituted benzo[b]furans from 2-chlorophenols and terminal alkynes. This catalyst system was also applicable to the sequential one-pot synthesis of disubstituted benzo[b]furans from dichlorophenols via the Suzuki-Miyaura cross-coupling of chlorobenzo[b]furan with boronic acids. The use of two ligands, Cy-DHTP and XPhos, is the key to promoting the reactions. Mechanistic studies suggest that the Pd-Cy-DHTP catalyst is the active species in the Sonogashira cross-coupling step, while the Pd-XPhos catalyst accelerates the Suzuki-Miyaura cross-coupling step.

Palladium-catalyzed one-pot synthesis of polysubstituted furans from alkynoates and 2-yn-1-ols

Easily accessible propargyl vinyl ethers are found to be acyclic precursors to construct furan derivatives. According to the reactive behavior of the substrates and the regulation of reaction conditions, three synthetic routes to polysubstituted furans via palladium-catalyzed reactions of propargyl vinyl ethers in situ-prepared from alkynoates and 2-yn-1-ols are presented herein. These methods could have potential application in synthetic and pharmaceutical chemistry for its facilitation and accessible starting materials.

Palladium-Catalyzed One-Pot Synthesis of Pyrrole-Annulated Coumarin, Quinolone, and 7-Aza-indole Derivatives

An efficient one-pot approach for the synthesis of highly substituted pyrrolocoumarin, quinolone, and pyrrolopyridine derivatives has been achieved by palladium acetate catalyzed reaction in DMF through initially formed enamine from cyclic and acyclic ketones and 6-amino-5-bromocoumarin, 6-amino-5-bromo-1-methyl quinolone, and 2-amino-3,5-dibromopyridine, respectively.

Facile Preparation of Macrocycles with Triphenylamine Backbone via C–N Coupling Reaction

Abstract Cyclic oligomers composed of triphenylamine backbone were conveniently prepared via palladium-catalyzed one-pot synthesis. The condition for the preparation was optimized to give the cyclic oligomers with large ring sizes in good yield up to 73.7%. The type of base for the reaction dramatically influenced the yield of cyclic oligomers, and potassium tert-butoxide was the most effective for the cyclization. The composition of the cyclic oligomers was determined by high-performance liquid chromatography (HPLC) as a mixture of pentamer, hexamer, and heptamer. The cyclic pentamer was easily isolated by only recrystallization from tert-butyl methyl ether.

Palladium-Catalyzed Direct One-Pot Synthesis of Carbazoles

Palladium-Catalyzed Direct One-Pot Synthesis of Carbazoles

Palladium-Catalyzed One-Pot Enantioselective Synthesis of Arylglycines

A palladium-catalyzed one-pot enantioselective synthesis of arylglycines has been developed from ethyl glyoxylate, p-toluenesulfonyl isocyanate and arylboronic acids. A good scope of arylboronic acids can be used, including electron-withdrawing and electron-donating examples. The imino esters were prepared in situ by a [2+2] cycloaddition and were inspired by Holmes and co-workers (P. Hamley, A. B. Holmes, A. Kee, T. Ladduwahetty, D. F. Smith Synlett 1999, 29).

Palladium-Catalyzed One-Pot Synthesis of 2-Alkyl-2-arylcyanoacetates

A one-pot procedure for the synthesis of 2-alkyl-2-arylcyanoacetates based on a Pd(OAc)2/DPPF (DPPF = 1,1'-diphenylphosphino ferreocene)-catalyzed enolate arylation followed by in situ alkylation has been developed. This procedure tolerates a diverse range of aryl and heteroaryl bromides, and provides a rapid entry to a variety of 2-alkyl-2-arylcyanoacetates in good to excellent yield.

1,2-Bis(diphenylphosphino)carborane As a Dual Mode Ligand for Both the Sonogashira Coupling and Hydride-Transfer Steps in Palladium-Catalyzed One-Pot Synthesis of Allenes from Aryl Iodides

[reaction: see text] One-pot allene synthesis from aryl iodides 1 and propargyldicyclohexylamine 2 proceeded in the presence of Pd(2)(dba)(3).CHCl(3) catalyst (2.5 mol %), 1,2-bis(diphenylphosphino)carborane 5 (10 mol %), CuI (15 mol %), and Et(3)N (150 mol %) to give the corresponding allenes 4 in good to high yields. Electron-deficient bidentate phosphines, such as 1,2-bis(diphenylphosphino)carborane 5 and (C(6)F(5))(2)PC(2)H(4)P(C(6)F(5))(2), play the role of a dual mode ligand for both the Sonogashira coupling and hydride-transfer reactions.