78322-97-1

Upstream product

• 201230-82-2 carbon monoxide 
• 1591-31-7 4-iodo-biphenyl 
• 108-95-2 phenol 
• 1871-38-1 phenyl 4-chlorobenzoate 
• 98-80-6 phenylboronic acid 
• 3468-53-9 phenyl nicotinate 
• 92-66-0 4-bromo-1,1'-biphenyl 
• 591-50-4 iodobenzene 
• 92-92-2 biphenyl-4-carboxylic acid 
• 50-00-0 formaldehyd 
• 29263-69-2 4-(phenoxymethyl)-1,1'-biphenyl 
• 122-01-0 4-chloro-benzoyl chloride 
• 100-58-3 phenylmagnesium bromide 
• 64-18-6 formic acid 

Downstream Products

• 5123-05-7 2-([1,1'-biphenyl]-4-yl)-5,5-dimethyl-1,3,2-dioxaborinane 
• 92-67-1 4-phenylalanine 
• 7116-96-3 1-pentyl-4-phenylbenzene 
• 1900-85-2 phenyl p-methylbenzoate 
• 874-79-3 phenyl(propyl)sulfide 
• 644-08-6 4-Methylbiphenyl 
• 80359-63-3 ([1,1′-biphenyl]-4-ylmethyl)diphenylphosphine oxide 
• 2920-38-9 4-cyano-1,1'-biphenyl 
• 79447-11-3 [1,1'-biphenyl]-4-yl(4-methoxyphenyl)methanone 
• 144432-80-4 2-(biphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 92-52-4 biphenyl 

Relevant academic research and scientific papers

Suzuki-Miyaura cross-coupling of esters by selective O-C(O) cleavage mediated by air- And moisture-stable [Pd(NHC)(μ-Cl)Cl]2precatalysts: Catalyst evaluation and mechanism

The cross-coupling of aryl esters has emerged as a powerful platform for the functionalization of otherwise inert acyl C-O bonds in chemical synthesis and catalysis. Herein, we report a combined experimental and computational study on the acyl Suzuki-Miyaura cross-coupling of aryl esters mediated by well-defined, air- and moisture-stable Pd(ii)-NHC precatalysts [Pd(NHC)(μ-Cl)Cl]2. We present a comprehensive evaluation of [Pd(NHC)(μ-Cl)Cl]2 precatalysts and compare them with the present state-of-the-art [(Pd(NHC)allyl] precatalysts bearing allyl-type throw-away ligands. Most importantly, the study reveals [Pd(NHC)(μ-Cl)Cl]2 as the most reactive precatalysts discovered to date in this reactivity manifold. The unique synthetic utility of this unconventional O-C(O) cross-coupling is highlighted in the late-stage functionalization of pharmaceuticals and sequential chemoselective cross-coupling, providing access to valuable ketone products by a catalytic mechanism involving Pd insertion into the aryl ester bond. Furthermore, we present a comprehensive study of the catalytic cycle by DFT methods. Considering the clear advantages of [Pd(NHC)(μ-Cl)Cl]2 precatalysts on several levels, including facile one-pot synthesis, superior atom-economic profile to all other Pd(ii)-NHC catalysts, and versatile reactivity, these should be considered as the 'first-choice' catalysts for all routine applications in ester O-C(O) bond activation.

Ligand-Controlled C?O Bond Coupling of Carboxylic Acids and Aryl Iodides: Experimental and Computational Insights

Palladium-catalyzed cross-coupling reactions between carboxylic acids and aryl halides have several possible competitive pathways. Decarboxylative C?C bond coupling and C?H arylation are well established in the literature. However, direct C?O bond coupling between carboxylic acids and aryl halides has received little success. In this report, we describe a protocol for exclusive C?O bond formation, enabled by a bidentate N,N-ligand such as 1,10-phenanthroline. The reaction is general for a broad range of carboxylic acids and iodoarenes. Experimental evidence and computational results suggest a high energy barrier for the alternative pathway of decarboxylative carbon-carbon bond coupling. (Figure presented.).

Fluoride anion-initiated bis-trifluoromethylation of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane

The fluoride anion-initiated reaction of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane (Me3SiCF3) that results in the formation of O-silyl-protected 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols is reported. A phenoxide anion, generated during the trifluoromethylation of the phenyl carboxylate, also activates the Me3SiCF3, which permits a catalytic amount of the fluoride anion source to be used. Various functional groups, which can be used for further elaboration, are tolerated in the reaction.

Ester Transfer Reaction of Aromatic Esters with Haloarenes and Arenols by a Nickel Catalyst

A catalytic ester transfer reaction of aromatic esters with aryl halides/arenols was developed. The present reaction can transfer an ester functional group from certain aromatic esters to haloarenes. This ester transfer reaction involves two oxidative additions-one from the C-C bond of the aromatic ester and one from the C-halogen bond of haloarenes-onto a nickel catalyst. The utilization of a Ni/dcypt catalyst capable of cleaving both chemical bonds was a key for the reaction progress. Furthermore, naphthol-based aryl electrophiles were also applicable to the catalytic system via C-O bond activation.

Decarbonylative Methylation of Aromatic Esters by a Nickel Catalyst

A Ni-catalyzed decarbonylative methylation of aromatic esters was achieved using methylaluminums as methylating agents. Dimethylaluminum chlorides uniquely worked as the methyl source. Because of the Lewis acidity of aluminum reagents, less reactive alkyl esters could also undergo the present methylation. By controlling the Lewis acidity of aluminum reagents, a chemoselective decarbonylative cross-coupling between alkyl esters and phenyl esters was successful.

Rhodium-catalysed aryloxycarbonylation of iodo-aromatics by 4-substituted phenols with carbon monoxide or paraformaldehyde

Rhodium-catalysed phenoxycarbonylation of aryl iodides were carried out under carbon-monoxide atmosphere and in the absence of CO, using paraformaldehyde as an alternative surrogate for carbonylation reactions. Both strategies proved to be efficient for the synthesis of the corresponding phenyl esters. High pressure reactions provided the ester products with good selectivity, however lower activity was achieved compared to palladium containing systems. Using paraformaldehyde as carbon-monoxide source special reaction conditions are required, thus dramatic changes observed during optimisation reactions. Using in situ generated Rh-diphosphine catalyst systems, remarkable influence of ligand structure and solvent composition was observed on the activity and chemoselectivity. The substrate scope and the substituent effect were also investigated.

Method for synthesizing aromatic aldehyde, aromatic ketone and aromatic ester through catalytically oxidizing alkyl aromatic compound by iron

The invention discloses a method for synthesizing aromatic aldehyde, aromatic ketone and aromatic ester through catalytically oxidizing an alkyl aromatic compound by iron, and belongs to the technical field of catalytic synthesis. According to the method, a low-cost and environment-friendly iron catalyst is used under a normal pressure; under the action of hydrogen and silicon reagents serving as an accelerant and an oxidant, a side chain of an aromatic hydrocarbon is oxidized into a carbonyl group for generating the corresponding aromatic aldehyde, aromatic ketone and aromatic ester. The method for preparing the aromatic aldehyde, the aromatic ketone and the aromatic ester through a catalytic oxidation reaction, which is provided by the invention, has numerous advantages that a catalyst, reaction raw materials, the oxidant and a silicon reagent are wide in sources and good in stability and is low-cost and environment-friendly; the alkyl aromatic compound is metered to participate in a reaction; the reaction condition is mild; the compatibility of functional groups is good; the scope of application is wide; the reaction selectivity is good; in an optimized reaction condition, the separation yield of a target product can be up to approximately 95 percent.

Palladium-catalyzed Suzuki-Miyaura coupling of aryl esters

The Suzuki-Miyaura coupling is among the most important C-C bond-forming reactions available due to its reliability, chemoselectivity, and diversity. Aryl halides and pseudohalides such as iodides, bromides, and triflates are traditionally used as the electrophilic coupling partner. The expansion of the reaction scope to nontraditional electrophiles is an ongoing challenge to enable an even greater number of useful products to be made from simple starting materials. Herein, we present how an NHC-based Pd catalyst can enable Suzuki-Miyaura coupling where the C(acyl)-0 bond of aryl esters takes on the role of electrophile, allowing the synthesis of various ketone-containing products. This contrasts known reactions of similar esters that provide biaryls via nickel catalysis. The underlying cause of this mechanistic divergence is investigated by DFT calculations, and the robustness of esters compared to more electrophilic acylative coupling partners is analyzed.

Inherent vs Apparent Chemoselectivity in the Kumada-Corriu Cross-Coupling Reaction

The Kumada-Corriu reaction is a powerful tool for C-C bond formation, but is seldom utilized due to perceived chemoselectivity issues. Herein, we demonstrate that high-yielding couplings can occur in the presence of many electrophilic and heterocyclic functional groups. Our strategy is mechanically based, matching oxidative addition rates with the rate of syringe pump addition of the Grignard reagent. The mechanistic reason for the effectiveness of this strategy is uncovered by continuous-infusion ESI-MS studies.

Palladium-catalyzed alkoxycarbonylation of aryl halides with phenols employing formic acid as the CO source

An efficient palladium-catalyzed alkoxycarbonylation of aryl halides with phenols has been developed. Various aryl benzoates have been isolated in good to excellent yields with formic acid as the CO source. The reaction proceeds smoothly under mild conditions and good functional group tolerance was observed.