I. O. Kalinovskii

The palladium-catalyzed cross-coupling reactions of mesitylcopper with aryl iodides

Abstract Mesitylcopper reacts with aryl iodides containing both electron-with- drawing and electron-donating groups in the presence of 1 equivalent Bu 4 NX (X = Br, I) and 1 mol.% of PhPdI(PPh 3 ) 2 to give cross-coupling products in high yields.

Reactions of organometallic compounds, catalyzed by transition metal complexes. 8. Carbonylation of arylmercury compounds in the presence of palladium and rhodium

Conclusions1.It has been found that in the presence of iodide ion the carbonylation of arylmereury compounds R2Hg and RHgX (R=p-ClC6H4, Ph, p-MeC6H4, p-MeOC6H4, p-Me2NC6H4, p-H2NC6H4, o-HOC6H4, 2-thienyl; X=Cl, Br, OAc), catalyzed by palladium and rhodium complexes, proceeds under very mild conditions (1 atm CO, 20°C) to give high yields of symmetrical diaryl ketones.2.The effects of type of solvent and catalyst, and the type and amount of halide ion have been examined, and the optimum conditions for carbonylation have been found.

Reactions of organometallic compounds catalyzed by transition metal complexes. Communication 6. Reactions of organomercury compounds with acid chlorides in the presence of palladium, nickel, and rhodium complexes

Conclusions1.A study was carried out on the effect of solvent, catalyst, and halide ion additives on the acyldemetallation of organomercury compounds in the presence of palladium, nickel, and rhodium complexes. Optimal conditions were found for carrying out the acyldemercuration both for R2Hg and RHgX, where R=aryl and alkyl groups.2.Convenient methods were developed for the synthesis of substituted benzophenones, alkylaromatic, unsaturated, and heterocyclic ketones.

Coupling reaction of organomercury compounds with aryl halides catalyzed by palladium complexes

Conclusions1.Organomercury compounds R2Hg and RHgX [R=CH3, C4H3S (2-thienyl), 2,4,6-(CH3)3C6H2, p-CH3OC6H4, o-CH3OC6H4, p-CH3C6H4, Ph, p-ClC6H4; X=I, Br, Cl] enter coupling reactions with aryl halides ArY [Ar=p-NO2C6H4, m-NO2C6H4, o-NO2C6H2, p-NCC6H2, p-CH3COC6H4, p-CH3O2, 2,4-(NO2)2C6H3, 2,4,6-(NO2)3C6H2; Y=I, Br] in the presence of 1-3 eq. iodide or bromide ion and 1 mole % palladium complex to give the corresponding RAr in high yield.2.A study was carried out on the effect of the nature of the solvent, various additives, oxygen, and the ligand in the palladium complex on this reaction.

Reactions of organometallic compounds, catalyzed by transition metal complexes. 7. Oxidative demercuration of arylmercury in the presence of complexes of palladium and rhodium

Conclusions1.The effects of adding halide ion, type of solvent and catalyst on the oxidative demercuration of arylmercury compounds in the presence of palladium and platinum complexes have been studied.2.In the presence of halide ion, arylmercury compounds Ar2Hg and ArHgX (Ar=p-ClC6H4, Ph, P-MeC6-H4, p-MeOC6H4, p-Me2NC6H4, p-H2NC6H4, 2-thienyl; X=Cl, OAc) undergo oxidative demercuration catalyzed by palladium and rhodium complexes, under very mild conditions (20°C), to give symmetrical diaryls in high yields.

Arylation of heterocycles in the reaction of heterocyclic mercury derivatives in the presence of palladium complexes

A convenient method is proposed for the synthesis of aryl derivatives of heterocyclic compounds by the coupling reaction of heterocyclic mercury derivatives and tin derivatives with aryl and heteryl iodides in the presence of palladium complexes. In the case of organotin compounds, the reaction proceeds without the formation of side-products although mercury derivatives are usually more available.