Cinnamyl alkyl ketones

Group C 6 C3+C2 Phenylalkylketones, Cinnamylidene acetic adds, Cinnamyl alkyl ketones, Phenyl a-pyrones... 

Unstabilized enolates react with allylic carbonates in the presence of metalacyclic iridium-phosphoramidite catalysts. Although ketones and aldehydes have not yet been used directly as pronucleophiles with this catalyst system, silyl enol ethers [80] and enamines [81] react with linear allylic carbonates to form, after workup, p-branched, y-8 unsaturated ketones (Scheme 13). Both methods form products in high yield, branched selectivity, and enantioselectivity for a range of cinnamyl and alkyl-substituted allylic carbonates. However, the silyl enol ethers derived from aliphatic ketones reacted in lower yields than enamines derived from the same ketones. 

Alkylation. Zinc-mediated reaction of cinnamyl chloride with aldehydes and ketones in aqueous THE" and Barbier-type reactions involving perfluoroalkyl... 

The (SIPr)Pd(cinnamyl)Cl (SlPr= l,3-bis(2,6-diisopropyl phenyl)-4,5-dihydro imidazol-2-ylidene) catalysed anaerobic oxidation of aryl/alkyl, aryl/aryl, and alkyl/ alkyl secondary alcohols to the corresponding ketones in high yields has been achieved using aryl chlorides in toluene with f-BuONa. Domino Pd-catalysed synthesis of a-arylated ketones from secondary aryl alcohols in very good yields was also reported. " ... 

AUylation of the /3-ketoester 136 was achieved with good enantioselectivity using the Trost ligand 20. AUylation of the ketone 138 could also be achieved, and although trimethyltin chloride was usually added, it was not an essential feature for obtaining reaction, once the ketone had been deprotonated with lithium diisopropylamide. Alkylation of cinnamyl acetate 140 using the /3-ketophosphonate 141 has been carried out using a palladium/BINAP 17 catalyst (Scheme 30). ... 

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