Aryl ketones stannanes, carbonylation

Mann et al. showed that various acetophenones can be synthesized by carbonylative coupling of aryl triflates with SnMe4 [65]. Under mild conditions using the catalyst system Pd(OAc)2/dppp, good yields (70-94 %) were obtained (Scheme 4.32). In 2002 Mido and colleagues reported the palladium-catalyzed carbonylative coupling of tributyl(l-fluorovinyl)stannane with aryl halides and aryl triflates [66]. In the presence of a catalytic amount of palladium catalyst and CsF in DMF, aryl 1-fluorovinyl ketones were formed in good yields. 

Addition of tributylstannyl-lithium to crotonaldehyde and protection of the resulting alcohol with chloromethyl methyl ether gives the stannane (192), which reacts with both alkyl and aryl aldehydes RCHO to form specifically the t/rr o-hydroxy-enol ethers (193). These latter compounds have been used to prepare tra/i5-4,5-disubstituted butyrolactones by hydrolysis and subsequent oxidation. Palladium-catalysed carbonylation of RX in the presence of organotin species constitutes a useful synthesis of unsymmetrical ketones, and in the example reported this year RX is an arenediazonium salt. The reaction, which is basically an aromatic acylation, proceeds in good to excellent yield. Another Pd-catalysed reaction of aromatics, this time aryl bromides, is their reaction with acetonyltributyltin (194), prepared from methoxytributyltin and isopropenyl acetate, to give the arylacetones (195). ... 

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