Oxidative carbonylation of phenol

Oxidative carbonylation of phenol was studied. The activities of the catalysts and cocatalysts were compared. The effect of solvents and pressure on the yield of the target product was studied. Deceased Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1124–1128, June, 1999.     

Palladium-catalyzed enantioselective carbonylation reactions

Carbonylation, one of the most powerful approaches to the preparation of carbonylated compounds, has received significant attention from researchers active in various fields. Indeed, impressive progress has been made on this subject over the past few decades. Among the various types of carbonylation reactions, asymmetric carbonylation is a straightforward methodology for constructing chiral compounds. Although rhodium-catalyzed enantioselective hydroformylations have been discussed in several el...     

The carbonylation of phase-transfer agents

Quaternary ammonium halides, which are capable of forming relatively stable free radicals, can be carbonylated to carboxylic acids by reaction with carbon monoxide, cobalt carbonyl, methyl iodide, sodium hydroxide (5 N) and benzene.     

Double carbonylation of zirconocene-alkyne complexes

Zirconocene-alkyne complexes prepared from Cp2ZrBu2, phosphines and alkynes reacted with CO to give double carbonylation products, 4-hydroxycyclobuten-1-one derivatives after hydrolysis.     

Rhodium-catalyzed reductive carbonylation of iodobenzene

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Carbamate preparation by nitromethane carbonylation

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, p. 1190, May, 1988.     

Manganese-catalyzed ring-opening carbonylation of cyclobutanol derivatives

Herein, we report a manganese-catalyzed ring-opening carbonylation of cyclobutanol derivatives through cyclic CC bond cleavage. The reaction happens via a radical-mediated pathway to selectively generate 1,5-ketoesters. A variety of substrates with substituents on the aromatic ring reacted with linear alcohols of different chain lengths. Obtained aliphatic esters are very attractive since they are usually difficult to access.     

The nickel-catalysed carbonylation of 2-mercaptoethanol

2-Mercapthoethanol undergoes carbonylation in pyridine solution in the presence of oxygen and of [Ni(CO)₃Pyl as a catalyst to give cyclic O, S-ethylelnethiorcarbonate. The isolation of thiolatonickel compound [Ni(SCH₂CH₂OH)₂] by the oxidation of a solution containing [Ni(CO)₃Py] and 2-mercaptoethanol, and its reaction with carbon monoxide to give the cyclic thiocarbonate and [Ni(CO)₃Py] prove that the reaction proceeds in at least two steps.     

Toward transition metal-catalyzed carbonylation of methanol without HI as copromoter: catalytic exocyclic carbonylation of cycloimino esters

[reaction: see text] Initial studies of a rare exocyclic C-O bond carbonylation are reported. Under the catalysis of Co(2)(CO)(8) in the absence of HI as the copromoter, cycloimino esters are carbonylated to afford N-acyllactams in high yields under relatively mild conditions (100-160 degrees C and 200-1000 psi). The reaction is interesting because it opens up the possibility of carbonylation of alcohols in the absence of HI.     

Oxidative carbonylation of styrene to ethyl cinnamate

A detailed study was made of the products of oxidative carbonylation of styrene in the presence of the catalyst system PdCl ₂ -CuCl ₂ -Cu(OAc) ₂ -Mn(OAC) ₂ at 100°C and 3.2 MPa. The target product, ethyl cinnamate, reached a molar proportion of 95%. The principal side reaction products were acetophenone and diethylphenyl succinate. Investigation of the influence of the composition of the catalyst system on the yield of target product and the selectivity of the reaction showed that Mn(OAc) ₂ was of greatest importance as a co-catalyst in the multicomponent Pd catalyst system. The results are discussed with reference to an alcoholate mechanism for oxidative carbonylation of olefins.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow 117912. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 552–557, March, 1992.     

Stille carbonylation of N-protected bromomethylindoles

A variety of N-protected indolylmethylbromides are carbonylated using 5 mol % Pd(PPh₃)₂Cl₂ under Stille conditions in the presence of an alcohol to afford the corresponding methyl/ethyl esters.     

五羰基铁催化羰化反应的研究进展

1827年,丹麦药剂师Zeise在加热PtCl2/KCl的乙醇溶液时得到了世界上第一个金属有机化合物,即后来人们命名的Zeise盐[1].1890年,Mond[1]等在研究一氧化碳（CO）对不锈钢阀门的腐蚀原因时发现：CO与镍粉反应生成的四羰基镍（Ni（CO）4）对阀门具有腐蚀作用．     

Amine synthesis via carbonylation reactions: aminomethylation

The preparation of aliphatic amines and alicyclic diamines by reaction of olefins, synthesis gas and dimethylamine, known as aminomethylation, was investigated. Synthesis involves homogeneous rhodium and ruthenium catalysts or mixtures thereof at very low concentrations. Employing 3–12 ppm Rh and 50–100 ppm Ru results in up to 97% selectivity towards the amines at conversions of up to 98% if aliphatic mono-olefins are used as starting materials. At high catalyst concentrations (173 ppm Rh, 2660 ppm Ru) the corresponding diamine is obtained from dicyclopentadiene in 89% yield. The influence of reaction parameters and catalyst ratios on the n/i-selectivity of the product indicates the scope as well as the limits of such a multi-step synthesis for a commercial process.     

Photopromoted carbonylation of bromobenzene under ambient conditions

The photopromoted carbonylation of bromobenzene with carbon monoxide catalyzed by inexpensive commercially available cobalt salts[Co(OAc)_2,CoCl_2]was carried out under ambient conditions.The results revealed that methyl benzoate was produced in the presence of basic additives(CH_3ONa,NaOAc or(n-C_4H_9)_3N).The catalytic activity of Co(OAc)_2was higher than that of CoCl_2.Furthermore,the activity of the carbonylation was greatly improved by addition of acetophenone,e.g.both the yield and selectivity of t...     

钯催化炔烃羰基化反应新进展

综述了过渡金属钯催化的炔烃羰基化反应最新研究进展，深入讨论了影响钯催 化的炔烃碳基化反应的区域选择性和立体选择性的两大因素：溶剂效应与酸碱效应。     

Mechanism of the carbonylation of dicyclopentadienylmolybdenum dihydride

The carbonylation of Cp₂MoH₂ proceeds through the intermediates Cp₂MoCO, [Cp₂Mo(H)CO] [CpMo(CO)₃] (I) and CpMo(CO)₃ to the final products [CpMo(CO)₃]₂ and CpMo(η³-C₅H₇)(CO)₂. The formation of I in the carbonylation reaction has been shown to involve net hydride transfer, but an alternate synthesis has demonstrated the considerable proton basicity of Cp₂MoCO. Since the net hydride transfer between Cp₂MoH₂ and [CpMo(CO)₃]₂ can be accelerated by production of metal centered radicals, the actual mechanism is not a simple two-electron process (H^? transfer, but rather a sequence of one-electron steps.     

Lactone synthesis based on atom transfer carbonylation

[reaction: see text] Five- to seven-membered lactones were prepared from omega-hydroxyalkyl iodides and CO by atom transfer carbonylation without the need for transition metal catalysts. The reaction proceeds via a hybrid radical/ionic mechanism in which the intramolecular alcoholysis of an omega-hydroxyacyl iodide, arising from atom transfer carbonylation, leads to the lactone.