Convenient Carbonylation of Aryl Bromides with Phenols to Form Aryl Esters by Applying a Palladium/Di‐1‐adamantyl‐n‐butylphosphine Catalyst

Abstract

Ester‐day once more: Palladium‐catalyzed carbonylation of aryl and heteroaryl bromides with phenols proceeds smoothly in the presence of di‐1‐adamantyl‐n‐butylphosphine (cataCXium® A). Twenty different aryl esters with a wide variety of substituents, are obtained in good to excellent yields under mild reaction conditions (0.1–0.2 MPa CO, 1 mol % Pd(OAc)2).

A General and Convenient Palladium‐Catalyzed Carbonylative Sonogashira Coupling of Aryl Bromides

“…Based on our recently developed palladium-catalyzed alkoxycarbonylation with phenols, [7] we investigated the carbonylative Sonogashira reaction of bromobenzene and phenyl acetylene with a catalyst system consisting of [(cinnamyl)PdCl] 2 (1 mol %) and BuPAd 2 (di-1-adamantyl-n-butylphosphine; cataCXium A; 6 mol %) in the presence of NEt 3 . Unfortunately, only 13 % of the desired carbonylative product at 45 % conversion was obtained (Table 1, entry 1).…”

Palladium‐Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide

“…[1] An important route to access these products is the carbonylation of aryl halides.S ince the seminal report from Heck and co-workers in 1974, [2] palladium-catalyzed carbonylation of aromatic halides has seen tremendous development. [1a,3] Most strategies make use of carbon monoxide as the carbonyl source in the presence of an appropriate nucleophile,f or example, alcohols,a mines,t hiols or organometallic species,f or alkoxycarbonylation, [3,4] aminocarbonylation, [3,5] carbonylative Heck, [3,6] carbonylative Suzuki-Miyaura, [3,7] and carbonylative Sonogashira. [3,8] However,d ue to the high toxicity and gaseous nature of carbon monoxide,t he application of catalytic carbonylation reactions on al aboratory scale remains underdeveloped.…”

Superior performance of Co-N/m-C for direct oxidation of alcohols to esters under air

“…However, these complicated reaction processes are usually accompanied by reagent waste and the production of a large number of undesired byproducts [1][2][3][4][5]. During recent decades, an enormous amount of effort has been focused on the development of cost-effective and environmentally friendly strategies for ester synthesis [6][7][8][9][10][11][12][13][14]. Of all the established methodologies, sin-gle-step direct oxidative esterification of alcohols, in which readily available alcohols are used as the starting materials instead of acids or their derivatives, is garnering increasing attention [15][16][17][18][19][20][21].…”