Solid TiCl3(OTf) catalyzed acetylation of alcohols, phenols and thiols with acetic anhydride in the absence of organic solvents at room temperature in a short reaction time. Benzoylation of alcohols, phenols and thiols also proceeded at higher temperature (similar to 80 degrees C) under solvent-free conditions. Transesterification of alcohols with ethyl acetate and ethyl formate was also carried out efficiently in the presence of this catalyst. Direct esterification of different alcohols with different carboxylic acids also Occurred readily ill the presence of this catalyst and in the absence of any organic solvents. (C) 2008 Elsevier B.V. All rights reserved.