Catalyzed Carbonylation Reactions Research Articles

Co-ordination chemistry and metal catalysed carbonylation reactions using 8-(diphenylphosphino)methylaminoquinoline: a ligand that displays monodentate, bidentate and tridentate co-ordination modes

Reaction of (diphenylphosphino)methanol with 8-aminoquinoline gives a novel potentially tridentate ligand, 8-(diphenylphosphino)methylaminoquinoline. The co-ordination chemistry of this ligand has been studied. Reaction with [Cp*RhCl2]2 gave a P-monodentate complex that was characterised by X-ray crystallography. On addition of one equivalent of silver salts, a 50 ∶ 50 mixture of a tridentate dicationic complex and the starting material is formed. We describe this somewhat unusual co-ordination behaviour as 2/3 labile. If two equivalents of silver salts are used, the tridentate complex can be isolated and fully characterised. Iridium, ruthenium, palladium and platinum complexes are also described in which the ligand acts as mono- bi-, and tri-dentate. The ligand was also tested as a stabilising ligand in palladium and rhodium catalysed carbonylation reactions.

Carbon monoxide activation in homogeneously catalysed reactions: the nature and roles of catalytic promotersBased on the presentation given at Dalton Discussion No. 4, 10–13th January, 2002, Kloster Banz, Germany.

One of the outstanding problems and challenges in CO activation concerns the lack of a detailed mechanistic understanding of the roles of catalytic promoters used in a number of homogeneously catalysed carbonylation reactions. These problems, and attempts at their resolution, are highlighted with reference to (i) the varied range of promoters that have found use in composite catalysts for the direct synthesis of oxygenates such as ethylene glycol and ethanol from CO/H2, (ii) the promotional effects of N-bases in the catalytic methoxycarbonylation of alkenes to esters, and (iii) some preliminary 13C NMR spectroscopic evidence which is enabling the definition of a dual role of Ru-promoters as iodide abstraction agents in the Ir-catalysed carbonylation of methanol to ethanoic (acetic) acid. The detection, and characterisation in solution, of an iodide-bridged Ru–Ir dimer is facilitating the development of a plausible, internally consistent model on which to base the catalysis.

Catalytic Carbonylation Reactions of Benzyne Derivatives

Catalytic Carbonylation Reactions of Benzyne Derivatives

ChemInform Abstract: Palladium(II)‐ and Rhodium(III)‐Catalyzed Carbonylation Reaction of Aryltin Compounds.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Palladium(II)- and Rhodium(III)-Catalyzed Carbonylation Reaction of Aryltin Compounds

Abstract A variety of aryltin compounds can be employed for carbonylation reactions in the presence of a catalytic amount of palladium(II) salt with reoxidant in acetonitrile or acetic acid under an atmospheric pressure of carbon monoxide (CO) to afford arenecarboxylic acids and diaryl ketones. Similar reactions also proceed by using rhodium(III) salt as a catalyst, where the presence of reoxidant is sometimes not necessary. More than one of two, three, or four aryl groups of aryltin compounds, and almost all of them in some cases, can be transferred to the products in this catalytic carbonylation.

ChemInform Abstract: Highly Efficient Synthesis of Steroidal Hydroxamic Acid Derivatives via Homogeneous Catalytic Carbonylation Reaction.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Mechanistic study of the Ru 3(CO) 12/chloride catalyzed carbonylation reactions of nitroarenes to carbamates and ureas; the role of the alkylammonium cation

The effect of the chloride countercation on the mechanism of the Ru 3(CO) 12/chloride catalyzed carbonylation of nitroarenes to carbamates has been investigated. The reason for the higher activity and selectivity obtained with tetraethylammonium chloride with respect to [PPN][Cl] is due to the higher igroscopicity of the former (only when no aniline is added) and to its ability do decompose to yield triethylamine. The role of this last compound is twofold. On one hand, it accelerates the alcoholysis of the intermediately formed diarylurea. On the other, it favors a reaction pathway that consumes aniline together with nitrobenzene, thus converting a by-product into the desired product.

Highly Efficient Synthesis of Steroidal Hydroxamic Acid Derivatives via Homogeneous Catalytic Carbonylation Reaction

Steroidal hydroxamic acid derivatives were synthesized in moderate to high yields by palladium-catalyzed carbonylation reactions of the corresponding iodo-alkenyl compounds or enol triflates in the presence of substituted hydroxylamines under mild reaction conditions. The effect of reaction parameters on the regioselectivity of carbonylation of N-substituted hydroxylamines is investigated in detail.

Platinum complexes of heteroannularly bridged heterobidentate ferrocenyl diphosphine ligands: their molecular structure and their use in catalytic carbonylation reactions

Platinum complexes PtCl 2(L) and PtCl(SnCl 3)(L) of the ferrocenyl diphosphine ligands (L) ( R, R)-1-diphenylphosphino-2,1′-[(1-diphenylphosphino)-1,3-propanediyl]-ferrocene ( 1), ( R, R)-1-diphenylphosphino-2,1′-[(1-dicyclohexylphosphino)-1,3-propanediyl]-ferrocene ( 2), ( R, R)-1-bis(4-fluorophenyl)phosphino-2,1′-[(1-diphenylphosphino)-1,3-propanediyl]-ferrocene ( 3), have been synthesised. Complexes PtCl 2( 1) and PtCl 2( 2) have been structurally characterised by X-ray diffraction. Both the ‘preformed’ and the in situ catalysts have been used in hydroformylations of styrene. At low temperature (below 70°C) and with use of the platinum catalysts the prevailing formation of ( R)-2-phenyl-propanal was observed, while at higher temperatures the formation of the ( S)-enantiomer was favoured. The palladium catalysts proved to be rather inactive in the hydromethoxycarbonylation of styrene. In the presence of ligand 2 the predominant formation of the linear regioisomer was observed.

Catalytic carbonylation for the synthesis of chemical intermediates

Chemistry related to three catalytic carbonylation reactions is discussed. Synthesis of diphenylurea from nitrobenzene, aniline, and CO gives isolated yields above 98% at 100–120 °C and 15–60 bar of CO in the presence of a palladium (II) complex, PPh3 and NEt4Cl. Experimental evidence was provided to prove a new reaction stoichiometry and involvement of a carbamoyl intermediate. In carbonylation of HCHO over ion exchange resin catalysts, reaction temperature, time, pressure, and solvent were important variables to obtain high yields of methyl glycolate. Carbonylation of isobutylphenylethanol at 120°C and 40 bar of CO in the presence of PdCl2−PPh3−HCl gives 98% yield of α-(4-isobutylphenyl) propionic acid (ibuprofen). Each catalyst component had a definite role that is indispensable for an efficient overall reaction.

Ru3(CO)12-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

A ruthenium-catalyzed carbonylation at a C-H bond in a benzene ring is described. The reaction of pyridylbenzenes with CO (20 atm) and ethylene in toluene at 160 degrees C in the presence of a catalytic amount of Ru(3)(CO)(12) results in propionylation at an ortho C-H bond in the benzene ring. Carbonylation does not occur at the pyridine ring, although this is necessary as a directing group to promote the reaction. Olefins such as trimethylvinylsilane and tert-butylethylene in place of ethylene can also be used in this reaction, however 1-hexene, cyclohexene, allyltrimethylsilane, styrene, methyl methacrylate, vinyl acetate, triethoxyvinylsilane, and isopropenyltrimethylsilane do not afford the coupling products. Transition metal complexes, other than ruthenium carbonyl, examined thus far, do not show catalytic activity. In the reaction of meta-substituted pyridylbenzenes, such as those having Me, OMe, CF(3), and COOMe group at the meta position in the benzene ring, carbonylation takes place at the less hindered C-H bond exclusively, irrespective of the electronic nature of the substituents. It is apparent that steric factors are more important for the control of regioselectivity. The reaction is also applicable to naphthyl and thienyl rings. Six-membered heterocycles, such as 2-pyrimidine and 4-pyrimidine, are also effective directing groups for carbonylation at a C-H bond in the benzene ring. The present reaction represents the first, effective catalytic carbonylation reaction involving cleavage of the benzene C-H bond.

Stereospecific synthesis of 4-carboxyphenylalanine and derivatives for use in Fmoc-based solid-phase peptide synthesis

Starting from N α-benzyloxycarbonyl-L-tyrosine( O-triflate)benzyl ester, we have prepared enantiomerically pure 4-carboxyphenylalanine and 4-methoxycarbonylphenylalanine derivatives using palladium (0) catalyzed carbonylation reactions. These unnatural amino acids were suitably protected and were used in solid-phase peptide synthesis using the Fmoc/ t-butyl approach.

Synthesis of phenolic natural products using palladium catalyzed coupling reactions

Derivatives of 2,4-diiodophenol are shown to undergo palladium catalyzed carbonylation and alkyne coupling reactions in excellent to moderate yield and high regioselectivity. The scope of these reactions is explored. Palladium catalyzed reactions are employed as the key steps in the synthesis of three phenolic natural products: Plicatin B, Drupanin and Eutypine.

A short and efficient synthesis of echiguanines A and B: Potent inhibitors of phosphatidylinositol-4-kinase

An efficient synthesis which utilizes a palladium catalyzed carbonylation reaction between 2-pivaloyl-7-iodo-7-deazaguanine and 3-aminopropionitrile as a key step was developed for the preparation of a new class of pyrrolopyrimidine based PI4-Kinase inhibitors: Echiguanines A and B.

ChemInform Abstract: Lanthanoid‐Promoted and Nickel Cyanide Catalyzed Carbonylation Reactions Under Phase‐Transfer Conditions.

AbstractThe nickel cyanide and phase‐transfer catalyzed carbonylation of arylmethylchlorides (I) is promoted by lanthanoid salts, e.g. CeCl3 (or LaCl3).

ChemInform Abstract: Palladium(2+)‐Catalyzed Intramolecular Aminocarbonylation of 3‐Hydroxy‐4‐pentenylamines and 4‐Hydroxy‐5‐hexenylamines.

AbstractThe N‐tosyl‐3‐hydroxy‐4‐pentenylamine (I) undergoes intramolecular amination and Pd(II)‐catalyzed carbonylation reaction to form the fused lactone (IV).

ChemInform Abstract: New Synthesis of Benzindanone Derivatives by Carbonylation and Aromatization of Masked Aromatics.

AbstractThe cyclic ketone (IV) is prepared by Pd(0)‐catalyzed carbonylation reaction of the allyl halide (II) with the olefin (I).

ChemInform Abstract: Rhodium(I) Catalyzed Carbonylation Reactions of Halides and Ethers.

Chemischer InformationsdienstVolume 17, Issue 11 Preparative Organic Chemistry ChemInform Abstract: Rhodium(I) Catalyzed Carbonylation Reactions of Halides and Ethers. C. BUCHAN, C. BUCHANSearch for more papers by this authorN. HAMEL, N. HAMELSearch for more papers by this authorJ. B. WOELL, J. B. WOELLSearch for more papers by this authorH. ALPER, H. ALPERSearch for more papers by this author C. BUCHAN, C. BUCHANSearch for more papers by this authorN. HAMEL, N. HAMELSearch for more papers by this authorJ. B. WOELL, J. B. WOELLSearch for more papers by this authorH. ALPER, H. ALPERSearch for more papers by this author First published: March 18, 1986 https://doi.org/10.1002/chin.198611147Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue11March 18, 1986 RelatedInformation

Transition metal catalysed carbonylation reactions of primary alcohols

Proprietes catalytiques du ruthenium dans la conversion des alcools primaires ROH en esters RCO 2 R et comparaison avec les proprietes catalytiques du cobalt et du rhodium

Homogeneous and phase transfer catalyzed carbonylation reactions

Homogeneous and phase transfer catalyzed carbonylation reactions