The activity of titanium- and tin-silicate samples such as TS-1, TS-2, Ti-beta and Sn-MFI has been investigated for acylation and alkylation of silyl enol ethers under mild liquid-phase conditions. Silyl enol ethers successfully react with acetyl chloride and tert-butyl chloride under dry conditions in the presence of above catalysts to produce the corresponding acylated and alkylated products, respectively. In the case of acetylation reaction, two different nucleophiles with carbon-center (C-atom) and oxygen-center (O-atom) in silyloxy group of silyl enol ether reacts with acetyl chloride to give 1,3-diketone and ketene-ester, respectively. The selectivity for alkylation is always ca. 100% and no side products are formed. Among the various solvents investigated, anhydrous THF was found to be the suitable solvent for alkylation; whereas dichloromethane exhibited high selectivity for diketones for acylation. The formation of nucleophiles from silyl enol ethers appears to be the key step for successful acetylation and tert-butylation by nucleophilic reaction mechanism. Sn-MFI showed less activity than that observed over the titanosilicates. The observed catalytic activity is explained on the basis of "oxophilic Lewis acidity" of titanium silicate molecular sieves in the absence of H(2)O under dry reaction conditions. (C) 2011 Elsevier B.V. All rights reserved.