Carbonylation of Alkyl Halides

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 P position (Eq. 6.28).  

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Reaction of halo ketones or diazo ketones with boranes 10-112 Carbonylation of alkyl halides... 

CARBONYLATION OF ORGANIC HALIDES 6.6.1 Carbonylation of Alkyl Halides... 

Davies, S. G. et al., J. Organomet. Chem., 1990, 386(2), 195 This compound is air sensitive and decomposes explosively. Use of the more stable tetrabutylammonium salt as a reagent for carbonylation of alkyl halides is recommended. 

Free-Radical Carbonylation of Alkyl Halides in scC02... 

Carbonylation of alkyl halides to yield esters and lactones (Table 8.5)... 

Carbonvlation of Benzyl Halides. Several organometallic reactions involving anionic species in an aqueous-organic two-phase reaction system have been effectively promoted by phase transfer catalysts(34). These include reactions of cobalt and iron complexes. A favorite model reaction is the carbonylation of benzyl halides using the cobalt tetracarbonyl anion catalyst. Numerous examples have appeared in the literature(35) on the preparation of phenylacetic acid using aqueous sodium hydroxide as the base and trialkylammonium salts (Equation 1). These reactions occur at low pressures of carbon monoxide and mild reaction temperatures. Early work on the carbonylation of alkyl halides required the use of sodium amalgam to generate the cobalt tetracarbonyl anion from the cobalt dimer(36). 

Carbonylation of alkyl halides 0-105 Reaction between formates or form-amides and organometallic compounds... 

Reaction of halo ketones or diazo ketones with boranes 0-102 Carbonylation of alkyl halides 0-104 Reaction between acyl halides and organometallic compounds 0-105 Reaction between other acid derivatives and organometallic compounds... 

This compound is air sensitive and decomposes explosively. Use of the more stable tetrabutylammonium salt as a reagent for carbonylation of alkyl halides is recommended. 

Carbonylation of alkyl halides is rare. As an exception, AcOH is produced commercially by the Monsanto process from MeOH and CO using Rh as a catalyst in the presence of HI. In this process (Scheme 3.10), Mel is generated in situ from MeOH and HI and undergoes oxidative addition. Insertion of CO generates an acetylrhodium intermediate, and nucleophilic attack of water produces AcOH, regenerating the Rh catalyst and HI (or reductive elimination to give acetyl iodide and hydrolysis). 

A few half-sandwich complexes containing a CpCo unit are known some of them are of synthetic utility and will be discussed below. The [CpCo(CO)]2 anion (19 ) can be methylated with Mel to give a dimethyl derivative, [CpCoMe(CO)]2. This complex decomposes to produce acetone in high yield, a reaction that is reminiscent of the use of Fe(CO)4H in the carbonylation see Carbonylation) of alkyl halides. 

Carbonylation of Alkyl Halides, Using Carbon Monoxide and Alkali-... 

Carbonylation of Alkyl Halides, Alcohols, or Alkanes Alkoxycarbonyl-de-halogenation... 

Palladium chloride and metallic palladium are useful for carbonylating olefinic and acetylenic compounds. Further, palladium is active for decarbonylation of aldehydes and acyl halides. Homogeneous decarbonylation of aldehydes and acyl halides and carbonylation of alkyl halides were carried out smoothly using rhodium complexes. An acyl-rhodium complex, thought to be an intermediate in decarbonylation, was isolated by the oxidative addition of acyl halide to chlorotris(triphenylphosphine)rhodium. The mechanisms of these carbonylation and decarbonylation reactions are discussed. 

In view of the fact that oxidative addition of alkyl halides and acyl halides to chlorocarbonylbis (triphenylphosphine) rhodium is possible, it was expected that the carbonylation of alkyl halides could be carried out catalytically with this complex. Actually the carbonylation of certain... 

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