1641-68-5

Upstream product

• 874-60-2 4-methyl-benzoyl chloride 
• 108-38-3 m-xylene 
• 34589-46-3 (2,4-dimethylphenyl)magnesium bromide 
• 104-85-8 para-methylbenzonitrile 
• 108-88-3 toluene 
• 21900-42-5 2,4-dimethylbenzoyl chloride 
• 99-94-5 p-Toluic acid 
• 1033133-20-8 potassium oxo(2,4-dimethylphenyl)acetate 
• 106-38-7 para-bromotoluene 
• 106-43-4 para-chlorotoluene 
• 201230-82-2 carbon monoxide 
• 624-31-7 4-tolyl iodide 

Downstream Products

• 782-23-0 2,7-dimethylanthracene 
• 99-94-5 p-Toluic acid 
• 108-38-3 m-xylene 

Relevant academic research and scientific papers

A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

PROCESS FOR PREPARING KETONES FROM ALPHA-OXO CARBOXYLATES AND ARYL BROMIDES

A process for preparing ketones of the general formula (III) where R is an optionally substituted carbocyclic aromatic radical having 6 to 24 carbon atoms or an optionally substituted alkyl radical or an optionally substituted heteroaromatic radical having 5 to 24 carbon atoms, andR1 is an optionally substituted carbocyclic aromatic radical having 6 to 24 carbon atoms or an optionally substituted heteroaromatic radical having 5 to 24 carbon atoms, by reacting alpha-oxo carboxylates of the general formula (I) wherein n and m is a number in the range from 1 to 6, M(m+) is a cation, and R has the meaning indicated for formula (III), with aryl bromides of the general formula (II) [in-line-formulae]R1—Br ??(II)[/in-line-formulae] where R1 has the meaning indicated for formula (III), in the presence of two transition metals or compounds thereof as catalyst, is described.

Palladium/copper-catalyzed decarboxylative cross-coupling of aryl chlorides with potassium carboxylates

(Chemical Equation Presented) Even non-activated aryl chlorides undergo decarboxylative cross-coupling reactions in the presence of a catalyst system generated in situ from CuI, 1,10-phenanthroline, PdI2, and di(tert-butyl)biphenylphosphane. The new catalyst is useful for both the synthesis of biaryl compounds from aromatic carboxylates and the synthesis of aryl ketones from salts of α-ketocarboxylic acids (see scheme; FG=functional group; R=aryl, alkyl).

Synthesis of ketones from α-oxocarboxylates and aryl bromides by Cu/Pd-catalyzed decarboxylative cross-coupling

(Chemical Equation Presented) The power of two metals: A Pd/Cu catalyst system mediates the in situ formation of acyl nucleophiles by decarboxylation of readily accessible and stable salts of α-oxocarboxylic acids and their cross-coupling with aryl or heteroaryl bromides to give ketones. The reaction may be usedin the presence of many functional groups and provides good yields.

Unsymmetrically substituted 2,7-dimethyl-1,8-diarylanthracenes

A synthesis has been developed for 2,7-dimethyl-1,8-di-o-tolylanthracene 4. The cis 4a and trans 4b isomers of this hydrocarbon can be separated and are stable to interconversion at temperatures below 200 °C. The two enantiomers of the trans isomer 4b have chiral cavities and are expected to be useful precursors for chiral reagents or chiral catalysts.

Carboxylic Trifluoromethanesulfonic Anhydrides as Highly Effective Acylation Agents. - Perfluoroalkanesulfonic Acid Catalyzed Acylation of Arenes

Arene- and alkanecarboxylic trifluoromethanesulfonic anhydrides 2 and 5 are highly effective acylation agents, which react without Friedel-Crafts catalysts even with deactivated aromatics to yield aryl ketones 3 and 6, respectively.Acylation of arenes with carbonyl chlorides 4 and catalytic amounts of perfluoroalkanesulfonic acid gives ketones 3 and 6, resp., in good yields.Under similar conditions other strong Broensted acids show a considerably smaller degree of catalytic effect.