Carbonylation, palladium-catalysed

A palladium-catalysed carbonylative Sonogashira coupling was successfully carried out in the same setup [35]. Aryl iodides and phenylacetylene were submitted... 

Skoda-Foldes R, Kollar L (2002) Synthetic applications of palladium catalysed carbonylation of organic halides. Curr Org Chem 6(12) 1097-1119... 

Kaiser, N.F.K., Hallberg, A. and Larhed, M In situ generation of carbon monoxide from solid molybdenum hexacarbonyl a convenient and fast route to palladium-catalysed carbonylation reactions, J. Comb. Chem., 2002, 4, 109-111. 

It is reported that the palladium-catalysed intramolecular aromatization of 1,1 -dichloro-9/T-fluoren-9-yIidene (15) may lead to the formation of fullerene fragments.89 The amiulation reaction, under palladium catalysis, between iodoanflines and ketones may yield indole derivatives.90 There have also been studies of the palladium-catalysed carbonylation of o-iodophenols with allenes which may lead to l-benzopyran-4-one derivatives,91 of the intramolecular coupling of phenols with aryl halides,92 and of the intramolecular Heck aiylation of cyclic enamides.93... 

The application of organozinc iodides prepared in THF is illustrated in Protocols 4 and 5, which describe the palladium catalysed cross-coupling of a serine-derived organozinc iodide with a vinyl iodide, and the palladium catalysed carbonylative cross-coupling of another serine-derived organozinc iodide with a functionalized aromatic iodide. In the reaction with the vinyl iodide, it is important to transfer the solution of the organozinc iodide from the residual zinc, since this can react unproductively with the electrophile. In the case of the carbonylative coupling with the functionalized aromatic iodide, such a transfer is unnecessary, since the zinc does not react with the electrophile under the reaction conditions. These two protocols also illustrate how to conduct such reactions on different scales. 

Nickel or palladium catalysed carbonyl addition and related reactions... 

A novel palladium-catalysed carbonylation of iodobenzene has recently been linked to base-induced coupling and cyclization with o-phenylenediamine, to give 2-arylbenzimidazoles without having to use an aryl carboxylic acid (Scheme 3.1.13). Provided that bases with pATa values around 6.6 are used, the yields of 2-arylbcnzimidazoles lie in the range 70-98%. This route is tolerant of a variety of functional groups and complements the classical approaches where the required benzoic acids arc not readily available [85]. 

Palladium-catalysed carbonylation of halides, with carbon monoxide, can be used to prepare esters, amides and ketones by trapping the intermediate acylpalladium halide with alcohols,amines and organometal-lics, respectively. Boronic acids are probably the best organometallics for the preparation of ketones, but conditions must be adjusted to give the best selectivity between the acylation reaction and simple Suzuki coupling of the boronic acid with the starting halide. ... 

A new synthesis of diazepam has been achieved, via the palladium-catalysed carbonylation of (105) to give (106), which was further converted into diazepam by a known route. ... 

Interactive mechanism for palladium-catalysed carbonylative butenolide formation... 

Orsellinic Acid Macrolides. - Palladium-catalysed carbonylation of an aryl... 

The palladium catalysed carbonylative cyclisation of (i)-iodoalkenes normally gives exo-methylene products however in a methanol-containing reaction mixture the initially formed alkyl palladium species will add a second equivalent of carbon monoxide to give keto-ester products [equation (27)]. ... 

There has been a review of palladium-catalysed carbonylative coupling reactions of aryl halides with carbon nucleophiles in the presence of carbon monoxide. It has been shown that rhodium is an efficient catalyst for the homocoupling reaction of arylzinc compounds in the presence of 1 atm of carbon monoxide to give diaryl ketones. Under similar conditions, palladium and nickel catalysts yield biaryls. The beneficial catalysis by rhodium is likely to derive from the ease of migration of the aryl ligand to carbon monoxide in the rhodium(III) intermediate. A rhodium catalyst has also been used in the formation of indole-3-carboxylates by reaction of indoles with alcohols in the presence of carbon monoxide. The catalytic cycle. Scheme 5, is likely to involve metallation of the indole at the 3-position, followed... 

Carbonylation of allyl bromides and chlorides has been achieved in presence of a nickel catalyst in aqueous NaOH at atmospheric pressure. Subsequently it is found that Palladium-catalysed carbonylation of allyl chloride proceeded smoothly in two-phase aqueous NaOH/benzene under atmospheric pressure at room temperature (Scheme 143). " ... 

Palladium-catalysed carbonylation of an iodoallylic alcohol, stereoselectively formed from the propargylic alcohol 4.57 through organoaluminium chemistry, was employed to form the base sensitive butenolide moiety of parviflorin 4.62 in a two-directional synthesis (Scheme After oxidative removal of the protecting... 

Alkynols 4.105 may be cyclized to a-methylene lactones 4.106 using palladium-catalysed carbonylation (Scheme 4.42)." The reaction is proposed to proceed via formation of an acyl palladium species 4.107, which undergoes intramolecular alkyne insertion. Protonolysis of the carbon-palladium bond of the vinyl complex 4.108 yields the product. 

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