2714-93-4

Upstream product

• 371-41-5 4-Fluorophenol 
• 98-88-4 benzoyl chloride 
• 1765-93-1 4-fluoroboronic acid 
• 100-52-7 benzaldehyde 
• 1227828-26-3 4-(triethoxysilyl)phenyl benzoate 
• 61807-37-2 benzoic acid 4‐iodophenyl ester 
• 18819-89-1 tetrabutylammonium benzoate 
• 644-32-6 dibenzoyl disulfide 
• 201230-82-2 carbon monoxide 
• 59-88-1 phenylhydrazine hydrochloride 
• 28547-23-1 4-(benzoyloxy)benzoic acid 
• 65-85-0 benzoic acid 
• 85909-02-0 N-benzyl-N-(tert-butoxycarbonyl)-benzamide 
• 352-34-1 4-fluoro-1-iodobenzene 

Downstream Products

• 371-41-5 4-Fluorophenol 
• 65-85-0 benzoic acid 
• 532-32-1 sodium benzoate 
• 371-35-7 sodium 4-fluorophenoxide 

Relevant academic research and scientific papers

Mechanically induced solvent-free esterification method at room temperature

Herein, we describe two novel strategies for the synthesis of esters, as achieved under high-speed ball-milling (HSBM) conditions at room temperature. In the presence of I2 and KH2PO2, the reactions afford the desired esterification derivatives in 45% to 91% yields within 20 min of grinding. Meanwhile, using KI and P(OEt)3, esterification products can be obtained in 24% to 85% yields after 60 min of grinding. In addition, the I2/KH2PO2 protocol was successfully extended to the late-stage diversification of natural products showing the robustness of this useful approach. Further application of this method in the synthesis of inositol nicotinate was also discussed. This journal is

Radical Decarboxylative Carbometalation of Benzoic Acids: A Solution to Aromatic Decarboxylative Fluorination

Abundant aromatic carboxylic acids exist in great structural diversity from nature and synthesis. To date, the synthetically valuable decarboxylative functionalization of benzoic acids is realized mainly by transition-metal-catalyzed decarboxylative cross couplings. However, the high activation barrier for thermal decarboxylative carbometalation that often requires 140 °C reaction temperature limits both the substrate scope as well as the scope of suitable reactions that can sustain such conditions. Numerous reactions, for example, decarboxylative fluorination that is well developed for aliphatic carboxylic acids, are out of reach for the aromatic counterparts with current reaction chemistry. Here, we report a conceptually different approach through a low-barrier photoinduced ligand to metal charge transfer (LMCT)-enabled radical decarboxylative carbometalation strategy, which generates a putative high-valent arylcopper(III) complex, from which versatile facile reductive eliminations can occur. We demonstrate the suitability of our new approach to address previously unrealized general decarboxylative fluorination of benzoic acids.

Hydrogen-bond-assisted transition-metal-free catalytic transformation of amides to esters

The amide C-N cleavage has drawn a broad interest in synthetic chemistry, biological process and pharmaceutical industry. Transition-metal, luxury ligand or excess base were always vital to the transformation. Here, we developed a transition-metal-free hydrogen-bond-assisted esterification of amides with only catalytic amount of base. The proposed crucial role of hydrogen bonding for assisting esterification was supported by control experiments, density functional theory (DFT) calculations and kinetic studies. Besides broad substrate scopes and excellent functional groups tolerance, this base-catalyzed protocol complements the conventional transition-metal-catalyzed esterification of amides and provides a new pathway to catalytic cleavage of amide C-N bonds for organic synthesis and pharmaceutical industry. [Figure not available: see fulltext.]

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.).

Palladium-catalyzed aryloxy- and alkoxycarbonylation of aromatic iodides in γ-valerolactone as bio-based solvent

Fossil-based solvents and triethylamine as a toxic and volatile base were successfully replaced with γ-valerolactone as a non-volatile solvent and K2CO3 as inorganic base in the alkoxy- and aryloxycarbonylation of aryl iodides using phosphine-free Pd catalyst systems. By this, the traditional systems were not simply replaced but also significantly improved. In the study, the effects of different reaction parameters, i.e. the use of several other solvents, the temperature, the carbon monoxide pressure, the base and the catalyst concentrations, were evaluated in details on the efficiency of the carbonylations. To gather some information on the mechanism of these reactions, the effects of the electronic parameters (σ) of various aromatic substituents of the aryl iodides as well as the influence of para-substitution of phenol were investigated on the activity. For a comparison, the aryl-substituted aryl iodides were also reacted with methanol and aryl iodide was also alkoxycarbonylated using several different lower alcohols. From the observed correlations between the electronic parameters of the aromatic substituents and the rates, it appears that the rate determining step is the oxidative addition of Ar–I to Pd0, provided that sufficient amounts of nucleophiles are present for the ester formation. If this is not the case, the rate of nucleophile attack might determine the overall rate.

Nickel-Catalyzed Cross-Coupling of Aryl Redoxactive Esters with Aryl Zinc Reagents

A nickel-catalyzed aryl-aroyloxyl C(sp2)-O radical cross-coupling reaction conducted using a redox active ester with aryl zinc reagent was developed. This method demonstrates a new disconnection approach for formation of aryl aryl esters. In the one-pot sequential process, the readily available aryl carboxylic acids can be converted into functionalized aryl aryl esters and heteroaryl esters. This protocol is amenable to the gram-scale synthesis. The present method has a wide substrate scope and high functional group tolerance.

Palladium-Catalyzed Aerobic Oxidative Coupling of Amides with Arylboronic Acids by Cooperative Catalysis

The first fluoride and palladium co-catalyzed conversion of amide to ester through an aerobic oxidative coupling pathway is reported. This new approach presents a practical process that employs easily available oxygen and commercially available arylboronic acids as coupling partners, uses a wide range of N- tosylamides, and proceeds under mild reaction conditions. This protocol demonstrates broad functional group tolerance, and provides an alternative option to synthesize esters from N-tosylamides which obtained by simply N-functionalization of secondary amides.

Enol Ester Intermediate Induced Metal-Free Oxidative Coupling of Carboxylic Acids and Arylboronic Acids

A facile, efficient and environmentally friendly methodology for the preparation of phenolic esters is realized via metal-free coupling of carboxylic acids and arylboronic acids. This sequential one pot reaction, employing methyl propiolate as an activating reagent, proceeds through the formation of enol ester intermediate, followed by a nucleophilic attack on the C-O bond under the oxidation of hydrogen peroxide. These studies display that enol esters, despite previously being overlooked as synthetic intermediates, would be the valuable building blocks for developing carbon–carbon and carbon–heteroatom bond-forming reactions.

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.

Preparation method for synthesis of phenolic ester through thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction

The invention discloses a preparation method for synthesis of phenolic ester through a thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction. Thiocarboxylic acid compounds andphenol compounds are subjected to a site specific reaction under certain conditions to produce phenolic ester compounds, wherein the certain conditions are as follows: under the conditions of normaltemperature, normal pressure and visible light, K2CO3 is used as an alkaline catalyst, terpyridyl ruthenium dichloride hexahydrate is used as a photosensitizer and acetonitrile is used as a reaction solvent. Synthesis of phenolic ester under catalysis of visible light is realized, thiocarboxylic acid is used as an acylation reagent, and the site specific phenol esterification reaction is realizedefficiently under mild conditions of normal temperature, normal pressure and visible light. The method has mild reaction conditions, large substrate functional group tolerance, high applicability andhigh yield, and an efficient, reliable and economical preparation method is provided for synthesis of phenolic ester.