Organomercury compounds acylation

Oxymercuration of simple alkyl- and acyl-substituted cyclopropenes generally results in ring opening.Addition of mercury(II) acetate to 3-methyl-3-phenylcyclopropene, however, gave a low yield of a cyclopropane containing organomercury compound (15-20%), which was converted into an isomeric mixture of 1 -methoxy-2-methyl-2-phenylcyclopropanes by reduction with lithium aluminum hydride. Reaction of 5 with mercury trifluoroacetate in methanol and then sodium hydroxide led predominantly to one cylopropane. ... 

Historically, the first report of the Pd-catalyzed cross-conpling reaction with acyl halide used organomercury compounds. " Although alkyl- and arylmercnry chlorides did not work, the use of dialkyl- and diarylmercury componnds gave the desired ketones in good yields. Acyl bromides are necessary to bring about fruitful results. The use of HMPA as the solvent is also unavoidable (Scheme 9). 

Mixed-metal catalysts based on 002(00)9 have proved effective In the synthesis of N acyl amlnoaclds, starting with either allylic alcohols, oxiranes (eqn.15) or trifluoropropene. The oxidative carbonylatlon of organomercury compounds Is subject to solvent effects. The Pd catalysed carbonylative cross-coupling of aryl Iodides with triIsobutylaluminium gives secondary benzyl alcohols a variety of functional groups are tolerated.Carbamate esters... 

Organomercury reagents do not react with ketones or aldehydes but Lewis acids cause reaction with acyl chlorides.187 With alkenyl mercury compounds, the reaction probably proceeds by electrophilic attack on the double bond with the regiochemistry being directed by the stabilization of the (3-carbocation by the mercury.188... 

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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