Transition Metal-catalyzed Carbonylation Reaction

A possible mechanism for this carbonylation might include  

When the palladium-catalyzed carbonylation with (PhSe)2 and CO is applied to 

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This review deals with the recent developments in the transition metal-catalyzed carbonylation reaction, especially hydroformylation, hydrocarbonylation, and oxidative hydrocarbonylation reactions of olefins, referring to literature since 1994. Because of the importance of carbonyl functionality in organic chemistry and the ideal atom efficiency of... 

The transition metal-catalyzed carbonylation reaction is an important pathway to introduce an extra carbon atom in the heterocyclic ring. Lu and Alper used this reaction with recyclable palladium-complexed dendrimers on silica to synthesize 1,4-oxazepines. Remarkably, starting from iodinated arylamine 121, as a substrate for the intramolecular carbonylation, quantitative conversion to the pentacyclic heterocycle 122, containing two oxazepine rings, was achieved (Equation 11) <2005JA14776>. 

Ruthenium is not an effective catalyst in many catalytic reactions however, it is becoming one of the most novel and promising metals with respect to organic synthesis. The recent discovery of C-H bond activation reactions [38] and alkene metathesis reactions [54] catalyzed by ruthenium complexes has had a significant impact on organic chemistry as well as other chemically related fields, such as natural product synthesis, polymer science, and material sciences. Similarly, carbonylation reactions catalyzed by ruthenium complexes have also been extensively developed. Compared with other transition-metal-catalyzed carbonylation reactions, ruthenium complexes are known to catalyze a few carbonylation reactions, such as hydroformylation or the reductive carbonylation of nitro compounds. In the last 10 years, a number of new carbonylation reactions have been discovered, as described in this chapter. We ex-... 

Transition-metal-catalyzed carbonylation reactions are useful one-carbon homologation techniques in organic synthesis, involving industrially important processes, for example, Fisher-Tropsch reaction, Monsanto acetic acid process, and hydroformylation (oxo reaction) [25]. 

The transition-metal-catalyzed carbonylation reaction has been extensively investigated, and especially the carbonylative ring expansion reaction of strained heterocycles has been shown to be a useful and efficient procedure to synthesize lactams, lactones, and thiolactones.203 The carbonylation of epoxides and aziridines 450 is a powerful tool to construct the /Mactone and /Mactam skeletons 451 (Scheme 142).204 This type of reactions can be regarded as a hetero-[3 + 1]-cycloaddition. 

Transition-metal-catalyzed carbonylation reactions have shown impressive progress during past few decades especially, the use of ruthenium, rhodium, and palladium as catalysts is widespread. More recently, iron and copper catalysts have also been attracting the attention of synthetic chemists because of their low cost and environmentally benign properties. 

M. Beller and X.-F. Wu, Transition Metal Catalyzed Carbonylation Reactions, DOI 10.1007/978-3-642-39016-6 l, Springer-Verlag Berlin Heidelberg 2013... 

Transition metal-catalyzed carbonylation reactions represent an enormous toolbox for CO-X bond formation (X = C, N, O, etc.). While most coupling reactions take place with heteronucleophiles nowadays, carbonylations including C-H activation are attracting more and more attention because the use of stoichiometric amounts of organometallic reagents can be avoided. 

There is an impressive number of publications on the application of transition metal-catalyzed carbonylation reactions in total synthesis. In 1980 Tsuji and colleagues applied palladium-catalyzed alkoxycarbonylation in the synthesis of Zearalenone [22] and Curvularin [23]. Starting from the corresponding aryl iodides or benzyl chlorides and alcohols, the parent molecules for Zearalenone and Curvularin were prepared in good yields and finally transferred to the target products by a few more steps (Scheme 10.1). 

In this chapter we have summarized and discussed the applications of transition metal catalyzed carbonylation reactions in total synthesis. A number of biologically active molecules have been synthesized by using carbonylation as one of the key steps. These examples of total synthesis greatly increased the values of carbonylation reactions and encouraged the basic methodology development in this area. 

Although some other examples of the transition-metal-catalyzed carbonylation reaction of carbon-carbon unsaturated compounds with thiols and CO have been reported, it is unclear whether these reactions involve the iyn-thiometallation process. 

Raoufmoghaddam S (2014) Recent advances in catalytic C-N bond formation a comparison of cascade hydroaminomethylation and reductive amination reactions with the corresponding hydroamidomethylation and reductive amidation reactions. Org Biomol Chem 12 7179-7193 Wu X-F, Fang X, Wu L, Jackstell R, Neumann H, Beller M (2014) Transition-metal-catalyzed carbonylation reactions of olefins and alkynes a personal account. Acc Chem Res 47 1041-1053... 

Doubtless, the hydroformylation reaction was the most investigated transition metal catalyzed carbonylation reactions in ionic liquids. This is mainly because of the industrial importance of this reaction that is in operation in various plants, which in some of them operates in aqueous biphasic regimes. The intense academic and industrial interest is mainly because of the limitations of the current aqueous-phase process to short-chain (heavier olefins in water for an effective and reasonable reaction rate to occur. 

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