Systematic study on the catalytic synthesis of unsaturated 2-ketocarboxamides: palladium-catalyzed double carbonylation of 1-iodocyclohexene

Palladium-catalyzed diaminocarbonylation: synthesis of androstene dimers containing 3,3′- or 17,17′-dicarboxamide spacers

“…This observation is in agreement with previous findings showing that 2-ketocarboxamide formation from iodoalkenes needs special conditions [36]. It has to be noted that the insertion of two carbon monoxides resulting in the formation of 2-ketoamide is general when aryl halides (preferably iodides and bromides) or aryl triflates are used as substrates [37].…”

One‐Step Synthesis of Dicarboxamides through Pd‐Catalysed Aminocarbonylation with Diamines as N‐Nucleophiles

“…Under these standard conditions, the catalytic aminocarbonylation of 3 with diamines a-f proceeded with complete conversion in 3 h, leading to the corresponding dicarboxamides 4a-4f in moderate isolated yields, ranging from 35 % (4b) up to 65% (4e), after workup and purification (Table 2, benzamide (4e) was obtained in significantly higher yield than all the other dicarboxamides linked by aliphatic chains, due to a lower tendency to formation of ketocarboxamide-type products when aromatic amines are used as nucleophiles. [32] A decrease in CO pressure to 1 bar did not substantially affect the reaction chemoselectivity, with isolated yields similar to those obtained under 10 bar of CO pressure being achieved ( Table 2, Entries 6 and 9 for 4c and 4e, respectively). In most cases, only the bis(carboxamides) 4a and 4c-4f were isolated in appreciable yields.…”

“…This observation is in agreement with previous findings that showed that iodoalkene substrates only undergo double carbon monoxide insertion under special conditions, such as higher carbon monoxide pressure (above 100 bar), lower temperatures (below 50°C) and/or in the presence of bulky π-acidic phosphite ligands. [32] However, the presence of aminomonocarboxamide products was detected by GC-MS and confirmed by NMR analysis of the reaction mixtures. The use of 2,6-diaminopyridine (f) as N-nucleophile resulted in a complex mixture of products, and the target dicarboxamide could not be isolated.…”

A New Tool in the Quest for Biocompatible Phthalocyanines: Palladium Catalyzed Aminocarbonylation for Amide Substituted Phthalonitriles and Illustrative Phthalocyanines Thereof

“…Our herein envisaged strategy uses 4-iodophthalonitrile (1) [53] as substrate and a range of amines as nucleophiles, in presence of a palladium catalyst formed in situ by addition of palladium(II) acetate to triphenylphosphine (in 1:2 molar ratio), together with Et 3 N as base and carbon monoxide as reagent (Table 1) [54,55]. Our studies began with the aminocarbonylation of 4-iodophthalonitrile (1) using glycine methyl ester hydrochloride (2a) as model nucleophile, to optimize reaction conditions (temperature, pressure of CO and time reaction parameters) in the palladium-catalyzed aminocarbonylation reaction ( Table 1).…”