A molecular precursor approach involving simple grafting procedures was used to produce site isolated titanium- supported epoxidation catalysts. The complexes [{ Ti(OiPr)(2)(OMent}(2)]) (1) and [Ti(OMent)(4)] (2) (MentO = 1 R,2S,5R-(-)-menthoxo) react with the remaining hydroxyl groups of SBA-15 after silanization with Me-3 SiCl, via loss of iPrOH and/or menthol and introduction of titanium species onto the silica surface. Grafting 1 and 2 onto SBA- 15 yields mostly isolated Ti(IV) sites, as evidenced by DRUV-vis. In addition, the silsesquioxane derivatives [Ti(OiPr)(2)(OMent){(c-C5H9)(7)Si8O13}] (3) and [Ti(OMent)(3) {(c-C5H9)(7)Si8O13}] (4) have been synthesized in order to compare the different homogeneous and heterogenous systems mentioned above in the asymmetric epoxidation of cinnamyl alcohol to evaluate their catalytic activity and enantioselectivity. (C) 2007 Elsevier B.V. All rights reserved.