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Various 1,3-disubstituted 2,3-dihydroimidazol-2-ones are readily prepared by the reaction of N,N′-disubstituted ureas with vicinal-diols in the presence of a catalytic amount of ruthenium complex in fair to good yields.

N-Aryl substituted formamides react smoothly with aminoarenes in the presence of a catalytic amount of dichlorotris(triphenylphosphine)ruthenium to afford various N,N′-diarylureas in good yields.

The addition of N-aryl substituted amides to non-activated terminal alkynes is efficiently promoted by the Ru3(CO)12–PCy3 catalyst system, affording the corresponding linear (E)-enamides in good yields with high regio- and stereo-selectivity.

Lanthanide(II) iodides such as Sml2 and Ybl2 show high catalytic activity for the photochemical allylation of aldehydes with allylic halides to give the corresponding homoallylic alcohols.

Dichlorobis(triphenylphosphine)palladium–tin(II) chloride system effectively catalyses the selective transformation of N-(2-nitrobenzylidene)amines into the corresponding 2H-indazole derivatives under carbon monoxide via a reductive N-heterocyclization reaction.

Tetrakis(triphenylphosphine)platinum(O) (Pt(PPh 3 ) 4 ) is an effective catalyst precursor for the carbonylative cross-coupling of alkyl iodides with sodium tetraphenylborate (NaBPh 4 ) which yields the corresponding alkyl phenyl ketones. In the reaction of n-hexyl iodide with NaBPh 4 , n-hexyl phenyl ketone was obtained in 60% yield.

Les nitroarenes et nitro-1alcanes reagissent avec l'acide acetique en presence de PtCl 2 (P(C 6 H 5 ) 3 ) combine au tetrachlorostannane (ou a d'autres acides de Lewis) pour donner les N-alkyl et N-aryl acetamides

The Ru3(CO)12-(CH3)3NO·2H2O catalyst system shows high catalytic activity for the hydroesterification of olefins, especially cyclohexene, with alkyl formates at 200 °C for 6 h under 20 kg cm−2 of carbon monoxide. The treatment of cyclohexene with benzyl formate afforded benzyl cyclohexane-carboxylate in 68% yield.

The carbonylation of acetylenic compounds is effectively catalyzed by a homogeneous platinum catalyst in alcoholic media. In the carbonylation of propargyl alcohol, ethyl 2-methylene-3-hydroxypropanoate was obtained in 68% yield at 100 °C under 80 kg cm−2 of initial carbon monoxide pressure. 3-Butyn-1-ol was selectively cyclocarbonylated to α-methylene-γ-butyrolactone in 84% yield. The internal acetylenic carbon of 1-octyne was selectively carbonylated to give methyl 2-methyleneoctanoate in 59% yield. Diphenyl-acetylene and 4-octyne afforded the corresponding mono-esters in 86% and 78% yields, respectively.

Various transition metal complexes including group VII and VIII metal carbonyls are highly active catalyst precursors for the photochemical carbonylation of organic iodides at room temperature under an atmospheric pressure of carbon monoxide. Primary, secondary and tertiary alkyl iodides which have β-hydrogens on sp3-carbons were smoothly carbonylated by this catalyst system without β-hydride elimination to give the corresponding esters in yields of 63 - 88 %.

Dodecacarbonyltriruthenium (Ru 3 (CO) 12 ) is an effective homogeneous catalyst precursor for the carbonylation of amines and hydroamidation of olefins under a carbon monoxide pressure of 40 kg cm −2 at 120–180°C. By the carbonylation of benzylamine, N -benzylformamide was obtained in 77% yield. 1-Octene was hydroamidated with benzylamine to N -benzylnonanamide in 67% yield (the selectivity to its linear isomer was 81%). These reactions appear to include ruthenium carbamoyl complex as the common key intermediate.

The following novel organic syntheses using group VIII metal complexes, especially iron, rhodium and ruthenium, which have been disclosed by the authors are reviewed.1) Highly selective reduction and carbonylation of a wide variety of organic compounds using alcoholic potassium tetracarbonylhydridoferrate (KHFe (CO) 4 (1)) as a reagent. 2) N-Alkylation and N-heterocyclization using amines and aldehydes mediated by 1, which provides novel synthetic methods for quinolines, benzimidazoles, isoindoles and isoindolines. 3) Rhodium and ruthenium catalyzed N-alkylation and N-heterocyclyzation of amines which involve the activation of N-H and O-H bonds. 4) Synthesis of aldehydes and ketones using K2Fe (CO) 4 reagent or ruthenium catalysts. 5) Ruthenium complex catalyzed novel carbon-carbon bond forming reactions using formyl derivatives which involve the catalytic activation of formyl C-H bond. 6) New methodology for carbonylation of alkyl iodides having β-hydrogens on saturated sp3 carbons is explored. Photo- and electrochemical carbonylations using various group VII and VIII metal complexes smoothly proceed under extremely mild conditions (i.e., at room tempeature and under 1 atm of CO (balloon)). The mechanisms of these novel reactions are suggested.

Dodecacarbonyltriruthenium (Ru 3 (CO) 12 ) showed high catalytic activity for the first one-to-one addition of N -substituted formamides to both terminal and internal olefins at 180-200°C under a carbon monoxide pressure of 20 kg cm −2 . The addition of N -metylformamide to cyclopentene afforded N -methylcyclopentanecarboxamide in 90% yield.

Ru 3 (CO) 12 -(CH 3 ) 3 NO·2H 2 O showed high catalytic activity for the decarbonylation of alkyl formates to the corresponding alcohols at 150 – 200 °C under an argon atmosphere. Decarbonylation of β-phenetyl formate afforded β-phenetyl alcohol in 82 % yield. On the other hand, when decarbonylation of benzyl formate was performed in the absence of (CH 3 ) 3 NO·2H 2 O, benzylation of arenes, which were employed as a solvent, proceeded via catalytic decarboxylation of benzyl formate. For the reaction of toluene with benzyl formate, phenyltolylmethane ( o -, m -, and p -mixture) was obtained in total 77 % yield.

Ruthenium complexes such as Ru 3 (CO) 12 and RuCl 3 · n H 2 O show high catalytic activity in the allylation of aldehydes by allylic acetates at 120°C to give homoallylic alcohols in good yields.

Various transition metal complexes including group VII and VIII metal carbonyls are highly active catalyst precursors for the photochemical carbonylation of organic iodides at room temperature under an atmospheric pressure of carbon monoxide. Primary, secondary and tertiary alkyl iodides which have β-hydrogens on sp3-carbons were smoothly carbonylated by this catalyst system without β-hydride elimination to give the corresponding esters in yields of 63 - 88 %.

Dodecacarbonyltriruthenium (RU 3 (CO) 12 ) and (η 4 -1,5-cyclooctadiene)(η 6 -1,3,5cyclooctatriene) ruthenium (Ru(COD)(COT)) catalyzed the hydroacylation of olefins with aldehydes at 180–200 °C for 48 h under 20 kgcm −2 of carbon monoxide to give unsymmetric ketones in good yields.

Ruthenium complexes such as Ru 3 (CO) 12 and RuCl 3 · n H 2 O show high catalytic activity in the allylation of aldehydes by allylic acetates at 120°C to give homoallylic alcohols in good yields.

[1-3-η-1-Methoxy-anti-2,3-bis(methoxycarbonyl)-prop-2-en-1-ylidene]tricarbonyliron (1) reacts with 2,2′-bipyridyl or 1,10-phenanthroline to give corresponding 2-ferracyclopent-4-en-1-one derivatives, 3d and 3e, in 45 and 80% yields respectively. Complex 3d crystallizes in the triclinic space group P 1 with a = 13.526(10), b = 15.71(2), c = 11.06(1) A , α = 91.51(10)°, β = 108.50(6)°, γ = 103.26(7)°, and Z = 4. Complex 3d has octahedral Fe(II) and two carbonyl group are in cis configuration; the acyl group and one of the bipyridyl nitrogen are in trans configuration.

Dodecacarbonyltriruthenium (RU 3 (CO) 12 ) and (η 4 -1,5-cyclooctadiene)(η 6 -1,3,5cyclooctatriene) ruthenium (Ru(COD)(COT)) catalyzed the hydroacylation of olefins with aldehydes at 180–200 °C for 48 h under 20 kgcm −2 of carbon monoxide to give unsymmetric ketones in good yields.