No Stirring Necessary:  Parallel Carbonylation of Aryl Halides with CO and Various Alcohols under Pressure

Abstract

The parallel carbonylation of aryl halides with 6-25 bar of CO in 1-mL vials in a standard autoclave was investigated. 4-Bromoacetophenone and 2-chloropyridine were used as model substrates with 102 different O-nucleophiles (primary and secondary alcohols, phenols). No inertization during the loading was necessary. Fifty esters (43 new, yield up to 60%) were isolated and characterized. Ether, ester, ketone, and sometimes even olefin functions were usually tolerated. The new method is suitable for screening and small scale products synthesis.

Palladium‐Catalyzed Carbonylation Reactions of Aryl Halides and Related Compounds

“…2-Chloropyridine was used as a model substrate by Blaser et al for the development of a simple parallel procedure for the carbonylation of aryl halides with alcohols and CO in standard autoclave equipment. [68] The methoxycarbonylation of heterocyclic chlorides was accomplished with PdCl 2 /(rac-binap) at 4.5 bar CO and 100 8C. [19] The excellent stability of the catalyst ensured that no side reactions occurred, and the methyl esters were isolated in good to excellent yields (60-99 %).…”

Polymer supported Pd catalyzed carbonylation of aryl bromides for the synthesis of aryl esters and amides

“…Heteroaryl bromides 3-bromopyridine and 3-bromothiophene also performed well in this reaction (Table 7, entries 11 and 12). Secondary amines, such as N-methyl aniline and morpholine were also tested with aryl bromides for the synthesis of the corresponding carbonylative products (Table 7, entries [13][14][15][16][17].…”

“…10 Carbonylation of the aryl halides in the presence of an alcohol is an attractive alternative method that tolerates a wide range of substrates, thus demonstrating a great advantage for the synthesis of substituted aromatic esters and its derivatives. [11][12][13] In this regard, various palladium-based catalytic systems have been explored for alkoxycarbonylation reaction. [14][15][16][17][18] Amides are also important chemicals that exist in pharmaceuticals, natural products, and many functional materials.…”

Palladiumkatalysierte Carbonylierungen von Arylhalogeniden und ähnlichen Substraten

“…Eine Erhöhung der Temperatur auf 150 °C führte selektiv zum Diester, der im 10‐mmol‐Maßstab hergestellt werden konnte. 2‐Chlorpyridin diente Blaser und Mitarbeitern als Modellsubstrat bei der Entwicklung eines einfachen Verfahrens zur parallelen Carbonylierung von Arylhalogeniden mit Alkoholen und CO in Standardautoklaven 68…”