31076-86-5

Upstream product

• 586-89-0 4-acetyl-benzoic acid 
• 108-95-2 phenol 
• 98-80-6 phenylboronic acid 
• 64-18-6 formic acid 
• 13329-40-3 4-Iodoacetophenone 
• 99-90-1 para-bromoacetophenone 
• 1864-94-4 phenyl formate 
• 201230-82-2 carbon monoxide 
• 50-00-0 formaldehyd 
• 591-50-4 iodobenzene 
• 31076-84-3 4-acetylbenzoyl chloride 
• 99-71-8 4-(1-methylpropyl)phenol 
• 98-88-4 benzoyl chloride 
• 13936-99-7 4-isopropylphenyl benzoate 

Downstream Products

• 18402-55-6 1-(4-(triethylsilyl)phenyl)ethan-1-one 
• 1443-80-7 4-cyanophenyl methyl ketone 
• 744238-47-9 C₁₅H₁₁BrO₃ 
• 127118-95-0 1-(4-(4-methylbenzoyl)phenyl)ethan-1-one 
• 99-92-3 p-aminobenzophenone 

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

Site-Specific Oxidation of (sp3)C-C(sp3)/H Bonds by NaNO2/HCl

A site-specific oxidation of (sp3)C-C(sp3) and (sp3)C-H bonds in aryl alkanes by the use of NaNO2/HCl was explored. The method is chemical-oxidant-free, transition-metal-free, uses water as the solvent, and proceeds under mild conditions, making it valuable and attractive to synthetic organic chemistry.

Conversion of esters to thioesters under mild conditions

We report conversion of esters to thioestersviaselective C-O bond cleavage/weak C-S bond formation under transition-metal-free conditions. The method is notable for a general and practical transition-metal-free system, broad substrate scope and excellent functional group tolerance. The strategy was successfully deployed in late-stage thioesterification, site-selective cross-coupling/thioesterification/decarbonylation and easy-to-handle gram scale thioesterification. Selectivity and computational studies were performed to gain insight into the formation of weak C-S bonds by C-O bond cleavage, which contrasts with the traditional trend of nucleophilic additions to carboxylic acid derivatives.

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.

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.

Mechanistic Insight into Weak Base-Catalyzed Generation of Carbon Monoxide from Phenyl Formate and Its Application to Catalytic Carbonylation at Room Temperature without Use of External Carbon Monoxide Gas

The mechanisms of the weak base-catalyzed generation of carbon monoxide (CO) and phenol from phenyl formate were investigated by experimental and theoretical methods. Kinetic studies revealed a first-order reaction in both phenyl formate and the base. The reaction was found to proceed by an E2 α-elimination pathway, which involves the abstraction of the formyl proton of phenyl formate, simultaneously generating CO and phenoxide. The reaction rate was affected by the substituents on phenyl formate, the polarity of solvents, and the basicity of bases. The mechanistic insight obtained from these studies permitted the chemical control of the rate of CO generation, which was the key to the development of the external CO-free Pd-catalyzed phenoxycarbonylation of haloarenes at room temperature. Because of the mild reaction conditions and wide substrate scope, this phenoxycarbonylation constitutes a general, safe, and practical method to synthesize arenecarboxylic acid esters. (Figure presented.).

Benzene-1,3,5-triyl triformate (TFBen): a convenient, efficient, and non-reacting CO source in carbonylation reactions

Benzene-1,3,5-triyl triformate (TFBen) as a kind of convenient and efficient CO source has been prepared for the first time. The character of TFBen as potent and non-reacting CO source has been proven by the successful synthetic applications in carbonylation reactions. Phloroglucinol (1,3,5-trihydroxybenzene) is abundant and naturally occurring has been applied as the reusable material for TFBen synthesis.

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.

Palladium nanoparticles immobilized on magnetic nanoparticles: An efficient semi-heterogeneous catalyst for carbonylation of aryl bromides

We describe a method for supporting palladium nanoparticles on magnetic nanoparticles modified with amino-functionalized dihydro-imidazolium groups. This catalytic system is very efficient in alkoxy- and amino-carbonylation reactions of aryl bromides. The catalyst can be easily recovered from the reaction mixture by applying an external magnetic field and reused for over five consecutive cycles without a significant decrease in its activity.