42582-53-6

Upstream product

• 24981-80-4 tetrakis(methyldiphenylphosphine)palladium 

Downstream Products

• 168097-38-9 Pd(P(C₆H₅)3)(P(C₆H₅)2CH₃)ICH₃ 
• 618-42-8 1-piperidin-1-yl-ethanone 
• 22381-22-2 1-(α-oxopropionyl)piperidine 
• 1696-20-4 4-acetylmorpholine 
• 38382-92-2 N,N-(tetramethylene-4-oxo) pyruvamide 
• 685-91-6 diethylacetamide 
• 22381-21-1 N,N-diethyl-2-oxo-propanamide 

Relevant academic research and scientific papers

Palladium-promoted double-carbonylation reactions. Reactions of organopalladium compounds with carbon monoxide and amines to give α-keto amides

A variety of mono- and diorganopalladium complexes, trans-PdR(X)L2 (R = Me, Et, and Ph; X = Cl, Br, I, and aryloxo; L = teritary phosphine ligand) and cis-PdMe2L2, react with carbon monoxide and secondary amines under mild conditions to give α-keto amides as double-carbonylation products. A series of acylpalladium complexes, trans-Pd(COR)X(PMePh2)2 (R = Ph, X = Cl, Br, and I; R = Me, X = Cl), the presumed reaction intermediates, were prepared, and their reactions with carbon monoxide and amines were investigated. The reaction of benzoylpalladium having bromo and iodo ligands with CO and amines proceeds more smoothly in a solvent of higher polarity than in nonpolar solvents, whereas the reaction with benzoyl(chloro)palladium complex takes place more readily in nonpolar solvents. On the basis of the effect of the solvent polarity on the reactions, two types of reaction pathways have been proposed: one involves an ionic acyl(carbonyl)palladium intermediate [PhCOPd(CO)L2]+X- attacked by amine to give acyl-carbamoyl species, from which α-keto amide is reductively eliminated, while the other mechanism proceeds through a neutral acyl-carbonyl intermediate [Pd(COR)(CO)XL]. Evidence to support the former mechanism has been obtained from the experiments using trans-[Pd(COPh)(CO)(PMePh2)2]ClO4, which is prepared by the treatment of trans-Pd(COPh)Cl(PMePh2)2 with AgClO4 and CO.

Mechanisms of 1,1-Reductive Elimination from Palladium

The 1,1-reductive elimination of ethane from three cis-bis(phosphine)dimethylpalladium complexes, L2Pd(CH3)2 (L = PPh3, PPh2CH3; L2 = Ph2PCH2CH2PPh2), and three trans analoques phenantrene (TRANSPHOS)> was carried out.The three cis complexes underwent reductive elimination in the presence of coordinating solvents (Me2SO, DMF, THF).The trans complexes which could isomerize to cis (L = PPh3, PPh2CH3) did so in polar solvents and then underwent reductive elimination. (TRANSPHOS)dimethylpalladium would not undergo reductive elimination of ethane, even at 100 deg C in Me2SO.The eliminations from the cis isomers were intramolecular as determined by the lack of crossover with the pentadeuteriomethylpalladium analogue and displayed first-order kinetics (k = 1.04 * 10-3 s-1, L = PPh3, 60 deg C; K = (6.5-9.5) * 10-5 s-1, L = PPh2CH3, 60 deg C; k = 4.78 * 10-7 s-1, L2 = Ph2PCH2CH2PPh2, 80 deg C).The presence of diphenylacetylene in the reaction mixture traps the palladium(0) product as the bis(diphenylmethylphosphine)(diphenylacetylene)palladium complex.Although (TRANSPHOS)dimethylpalladium would not undergo a 1,1-reductive elimination of ethane, the addition of CD3I to a Me2SO soliution of this complex at 25 deg C rapidly produced CD3-CH3, implicating a transient palladium(IV) intermediate.