6454-03-1

Upstream product

• 36748-88-6 3-iodobenzo[b]thiophene 
• 201230-82-2 carbon monoxide 
• 98-80-6 phenylboronic acid 
• 5381-20-4 benzothiophene-3-carboxaldehyde 
• 17763-67-6 Phenyl triflate 
• 95-15-8 Benzo[b]thiophene 
• 71-43-2 benzene 
• 65628-41-3 3-benzothienyl(phenyl)methanol 
• 36967-85-8 benzoyl triflate 
• 65-85-0 benzoic acid 
• 532-32-1 sodium benzoate 
• 7342-82-7 3-Bromothianaphthene 
• 98-88-4 benzoyl chloride 
• 536-74-3 phenylacetylene 

Relevant academic research and scientific papers

A palladium-catalyzed C-H functionalization route to ketones: Via the oxidative coupling of arenes with carbon monoxide

We describe the development of a new palladium-catalyzed method to generate ketones via the oxidative coupling of two arenes and CO. This transformation is catalyzed by simple palladium salts, and is postulated to proceed via the conversion of arenes into high energy aroyl triflate electrophiles. Exploiting the latter can also allow the synthesis of unsymmetrical ketones from two different arenes.

Aerobic oxidation of alcohols with air catalyzed by decacarbonyldimanganese

The oxidation of alcohols to carbonyl compounds using air as the terminal oxidant is highly desirable. As described in previous reports, the abstraction of α-H of the alcohol is the most important step, and it typically requires not only a metal catalyst but also complex ligands, co-catalysts and bases. Herein, we report a practical and efficient method for the oxidation of primary alcohols, secondary alcohols, 1,2-diols, 1,2-amino alcohols, and other α-functionalized alcohols using a commercially available catalyst, Mn2(CO)10, and no additives. Preliminary mechanistic studies indicated that an alkoxyl radical intermediate existed in our system, and a plausible mechanism consistent with the experimental results and literature was proposed.

Decarboxylation with Carbon Monoxide: The Direct Conversion of Carboxylic Acids into Potent Acid Triflate Electrophiles

We report a new strategy for the conversion of carboxylic acids into potent acid triflate electrophiles. The reaction involves oxidative carbonylation of carboxylic acids with I2 in the presence of AgOTf, and is postulated to proceed via acyl hypoiodites that react with CO to form acid triflates. Coupling this chemistry with subsequent trapping with arenes offers a mild, room temperature approach to generate ketones directly from broadly available carboxylic acids without the use of corrosive and reactive Lewis or Bronsted acid additives, and instead from compounds that are readily available, stable, and functional group compatible.

Generation of Aryl and Heteroaryl Magnesium Reagents in Toluene by Br/Mg or Cl/Mg Exchange

The alkylmagnesium alkoxide sBuMgOR?LiOR (R=2-ethylhexyl), which was prepared as a 1.5 m solution in toluene, undergoes very fast Br/Mg exchange with aryl and heteroaryl bromides, producing aryl and heteroaryl magnesium alkoxides (ArMgOR?LiOR) in toluene. These Grignard reagents react with a broad range of electrophiles, including aldehydes, ketones, allyl bromides, acyl chlorides, epoxides, and aziridines, in good yields. Remarkably, the related reagent sBu2Mg?2 LiOR (R=2-ethylhexyl) undergoes Cl/Mg exchange with various electron-rich aryl chlorides in toluene, producing diorganomagnesium species of type Ar2Mg?2 LiOR, which react well with aldehydes and allyl bromides.

A Nickel-Catalyzed Carbonyl-Heck Reaction

The use of transition-metal catalysis to enable the coupling of readily available organic molecules has greatly enhanced the ability of chemists to access complex chemical structures. In this work, an intermolecular coupling reaction that unites organotriflates and aldehydes is presented. A unique catalyst system is identified to enable this reaction, featuring a Ni0 precatalyst, a tridentate Triphos ligand, and a bulky amine base. This transformation provides access to a variety of ketone-containing products without the selectivity- and reactivity-related challenges associated with more traditional Friedel–Crafts reactions. A Heck-type mechanism is postulated, wherein the π bond of the aldehyde takes the role of the olefin in the insertion/elimination steps.

Synthesis of carbonylated heteroaromatic compounds: Via visible-light-driven intramolecular decarboxylative cyclization of o -alkynylated carboxylic acids

An efficient strategy for the easy access to carbonylated heteroaromatic compounds has been developed via a visible-light-promoted intramolecular decarboxylative cyclization reaction of o-alkynylated carboxylic acids. This method is characterized by its b

One-pot synthesis of heteroaryl and diheteroaryl ketones through palladium-catalyzed 1,2-addition and oxidation

A synthetic method was developed for the preparation of heteroaryl and diheteroaryl ketones from aldehydes and organoboronic acids through a palladium-catalyzed 1,2-addition and oxidation that uses an aryl iodide as the oxidant. This one-pot process shows high tolerance for a broad range of heterocyclic substrates by using 1.0-3.0 mol-% of the catalyst that is formed from allylpalladium chloride dimer and a thioether-imidazolinium chloride. In addition to fine-tuning the catalytic system, the use of a sterically hindered aryl iodide that has a substituent at the ortho position, such as 2-iodotoluene, is important to obtain the desired ketones with heterocyclic moieties in good to excellent yields. The one-pot synthesis of heteroaryl and diheteroaryl ketones was achieved by a palladium-catalyzed 1,2-addition and oxidation. This catalytic process with 1.0-3.0 mol-% catalyst loading tolerates a broad range of heterocyclic substrates to give ketones with heterocyclic moieties in good to excellent yields. Copyright

Mercury(II)-catalyzed cyclization of 2-alkynylphenyl alkyl sulfoxides provides 3-acylbenzo[b]thiophenes

Ring cyclization: A mercury-catalyzed cyclization reaction to provide 3-benzoylbenzo[b]thiophenes was achieved in good yields by treatment of 2-alkynylphenyl alkyl sulfoxides with mercury chloride and 2,3-dichloro-5,6- dicyano-1,4-benzoquinone (DDQ) in be

Method of preparing organomagnesium compounds

The present invention is directed to a reagent for use in the preparation of organomagnesium compounds as well as to a method of preparing such organomagnesium compounds. The present invention furthermore provides a method of preparing functionalized or unfunctionalized organic compounds as well as the use of the reagents of the present invention in the preparation of organometallic compounds and their reaction with electrophiles. Finally, the present invention is directed to the use of lithium salts - LiY in the preparation of organometallic compounds and their reactions with electrophiles and to an organometallic compound which is obtainable by the disclosed method.

Palladium-Catalyzed Carbonylative Cross-Coupling Reaction of Arylboronic Acids with Aryl Electrophiles: Synthesis of Biaryl Ketones

The carbonylative cross-coupling reaction of arylboronic acids with aryl electrophiles (ArI, ArBr, and ArOTf) to yield unsymmetrical biaryl ketones was carried out in anisole at 80°C in the presence of a palladium catalyst and a base. The reaction selectively proceeded under an atmospheric pressure of carbon monoxide when PdCl2(PPh3)2 (3 mol %)/K2CO3 (3 equiv) were used for aryl iodides and PdCl2(dppf) (3 mol %)/K2CO3 (3 equiv)/KI (3 equiv) for the bromides or the triflates. The carbonylation of arylboronic acids with benzyl halides gave aryl benzyl ketones.