Transition Metal Catalyzed Carbonylation

Transition-metal catalyzed carbonylation of 1-perfluoroalkyl-substituted 2-iodoalkanes has been carried out in aqueous media to give carboxylic acids with a perfluoroalkyl substituent at the (J> position (Eq. 6.28).61... 

Abstract Development in the field of transition metal-catalyzed carbonylation of epoxides is reviewed. The reaction is an efficient method to synthesize a wide range of / -hydroxy carbonyl compounds such as small synthetic synthons and polymeric materials. The reaction modes featured in this chapter are ring-expansion carbonylation, alternating copolymerization, formylation, alkoxycarbonylation, and aminocarbonylation. 

Transition-metal-catalyzed carbonylations are of great importance in organic synthesis as a powerful tool to prepare a variety of carbony compounds. Among them, hydroformylation has been most extensively studied not only in the laboratory but also in industry. Industrial production of alkanals from 1-alkenes... 

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... 

CASE STUDY TRANSITION-METAL CATALYZED CARBONYLATION... 

Case Study Transition-Metal Catalyzed Carbonylation of Methanol... 

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>. 

Metal complexes enable one to employ molecules that are thermally unreactive toward cycloadditions by taking advantage of their ability to be activated through complexation. Most of the molecules activated by transition-metal complexes involve C-C unsaturated bonds such as alkynes, alkenes, 1,3-dienes, allenes, and cyclopropanes. In contrast, carbonyl functionalities such as aldehydes, ketones, esters, and imines seldom participate in transition-metal-catalyzed carbonylative cycloaddition reactions. Recently, such a transformation was reported via the use of ruthenium complexes. 

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]. 

Transition-metal-catalyzed carbonylation of an iodide in the presence of an alcohol or water gives the ester or acid, respectively. Bis(triphenylphosphanyl)palladium dichloride and octa-carbonyldicobalt are efficient catalysts. Starting from diiodidc 16, dicarboxylic ester 17 or dicarboxylic acid 18 are obtained in good to excellent yield.The formation of 18 is a good alternative to the hydrolysis of an ester to an acid. ... 

The transition metal-catalyzed carbonylation of allylic compounds has been developed as a simple extension of carbonylations of benzylic derivatives. In this respect nickel cyanide has been used as a catalyst precursor for carbonylation of allyl... 

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. 

Few examples of stereoselective transition metal catalyzed carbonylative multicomponent cycloadditions leading to other than five-membered rings have been reported1 72. Typical is the reaction of 3,3-dimethylcyclopropene with carbon monoxide, catalyzed by a palladium(O) complex, to stereoselectively form hexamcthyltrishomotropone as a tetracyclic adduct l73. 

Transition-metal catalyzed carbonylation of 1-perfluoroalkyl-substituted... 

Because of the importance of the CO insertion into a transihon metal-carbon a-bond in relation to the transition metal-catalyzed carbonylation, the mechanism of the CO insertion has attracted considerable attenhon [1,2]. Through fundamental studies on model complexes, the route of CO insertion has been established for most transition metal complexes to be the one through alkyl migration mechanism [3-8]. While CO insertion can occur with various metal-heteroatom o-bonds, only insertion into metal alkyls (hydrocarbyls) will be discussed in this chapter. 

Metal Catalysts describes a number of asymmetric catalytic reactions, while nucleophilic activation of carbon monoxide and the application of metal carbonyl catalyzed water-gas shift (WGS) and related reactions to homogeneous catalysis have also been reviewed. A review on transition metal catalyzed carbonylations covers the year 1986. Reductions using ammonium formate as the reducing agent in the presence of homogeneous and heterogeneous nickel and palladium catalysts have been the subject of a recent survey. 

It is generally agreed that Roelen s discovery of the hydroformylation reactiont was the birth of the transition metal-catalyzed carbonylation. Initially, Co catalysts were most extensively used, but the Rh-based processes have since been developed as a superior methods. Although Pd may have been tested along with several other metals, such as Fe, Ru, and Ni, it has never been shown to be very useful in the hydroformylation reaction, sometimes called the oxo process. A publication in 1963 by Tsuji et al. on a related but clearly different reaction of alkenes with CO and alcohols in the presence of a Pd catalyst producing esters was one of the earliesL if not the earliesL reports describing a successful and potentially useful Pd-catalyzed carbonylation reaction. This was soon followed by the discovery of another Pd-catalyzed carbonylation reaction of allylic electrophiles with CO and alcohols ° (Scheme 7). 

Transition-Metal-Catalyzed Carbonylative Domino Reactions... 

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. 

Transition-Metal-CatalYzed Carbonylative Domino Reactions 119 pd) O... 

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