Microwave-assisted, Mo(CO)6-mediated, palladium-catalyzed amino-carbonylation of aryl halides using allylamine: from exploration to scale-up

Palladium‐Catalyzed Carbonylation Reactions of Aryl Halides and Related Compounds

“…[50] Very recently, a microwave-promoted palladium-catalyzed aminocarbonylation of (hetero)aryl halides (X = I, Br, Cl) using [Mo(CO) 6 ] and allylamine (45) as the nucleophile was also described. [51] Surprisingly, no side products resulting from the competing Heck reaction were detected. Aminocarbonylation was achieved for the first time on a larger laboratory scale (25 mmol) starting from 4-iodoanisole (44; Scheme 15).…”

Microwave irradiation as a sustainable tool for catalytic carbonylation reactions

“…Lower yields were obtained for the highly electron deficient 4-trifluoromethylphenylbromide and the sterically hindered 2-bromotoluene [49]. Palladium-catalyzed aminocarbonylation of several hetero-or aryliodides with allylamine was reported by Larhed [51], using Mo(CO) 6 as in situ CO source. In this case, they utilized DBU as base, and dioxane as solvent, under microwave heating, 125-140 °C for 10-15min, obtaining amides of type 51 (Scheme 23).…”

“…Heterocyclic iodides were also carbonylated, generating 2-thienyl-and 3-furyl derivatives in good yields, without generation of competitive Heck-reaction products [51]. Additionally, this reaction was also explored for scale-up process.…”

An Improved Protocol for Palladium‐Catalyzed Alkoxycarbonylations of Aryl Chlorides with Alkyl Formates

“…[6] With respect to aryl chlorides it should be noted that aminocarbonylations have also been achieved with Mo(CO) 6 under microwave activation. [7] Despite these studies, a more general method for the alkoxycarbonylation of aryl chlorides without using carbon monoxide is still desirable.…”

“…The isopropyl ester was formed in lower yield presumably because of steric reasons. (2) 0 0 [a] Reaction conditions: 1 mmol 3,4-dimethyl-1-chlorobenzene, 1 mL butyl formate, 0.5 mol% PdA C H T U N G T R E N N U N G (OAc) 2 , 0.07 mol% Ru 3 (CO) 12 , ligand as given, 120 mol% DBU (DBU = 2,3,4,6,7,8,9,…”