Organometallics acyl halides

Acyl halides react with organometallic reagents without catalysts, but sometimes the Pd-catalyzed reactions give higher yields and selectivity than the Lincatalyzed reactions. Acyl halides react with Pd(0) to form the acylpalladium complexes 846, which undergo facile transmetallation. 

The Conversion of Acyl Halides to Ketones With Organometallic Compounds ... 

Reaction between acyl halides and organometallic compounds 10-115 Reaction between other acid derivatives and organometallic compounds... 

Halogenation of alkenyl organometallic compounds Addition of hydrogen halides to triple bonds Halogenation of alkynes or allenes Addition of alkyl halides to triple bonds Addition of acyl halides to triple bonds... 

Organopalladium intermediates are also involved in the synthesis of ketones and other carbonyl compounds. These reactions involve acylpalladium intermediates, which can be made from acyl halides or by reaction of an organopalladium species with carbon monoxide. A second organic group, usually arising from any organometallic reagent, can then form a ketone. Alternatively, the acylpalladium intermediate may react with nucleophilic solvents such as alcohols to form esters. 

II c., Cl 0 M L- X c Reaction of acyl halides or other acid derivatives with 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... 

Organonitrogen-lithium compounds, and particularly lithium amides (R2NLi), are widely used both in organic and in organometallic syntheses. For the former, these strong bases are employed as proton abstractors (5-8), to generate new organolithiums. These can then be derivatized with so-called electrophiles, e.g., alkyl and acyl halides (E+ = R+ and R—C+=0) and trimethylsilylchloride (E+ = MeaSi+) [Eq. (1)]. 

Many other types of organometallics which are not acylated directly acid chlorides and which do not undergo addition to ketones may still transmetallate into the acylpalladiumfll) complex. Simple alkyl organomercurials have been acylated in this fashion to give moderate to good yields of ketones. " Larock has studied the palladium-catalyzed acylation of vinylmercury(II) compounds with acyl halides (equation 104). The reaction was only modestly productive and could not compare to the yield provided by aluminum chloride catalysis. 

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