Strong Organic Bases as Building Blocks of Mesoporous Hybrid Catalysts for C–C Forming Bond Reactions

1,8‐Bis(tetramethylguanidino)naphthalene (TMGN), a neutral organic base that combines the properties of guanidine and the properties of proton sponges, was used as a building block to produce organic–inorganic silica‐based mesoporous hybrids with strong basic properties. The TMGN‐based mesoporous hybrids (TMGN/SiO 2 ) were prepared by a sol–gel route working at a neutral pH and low temperatures, which avoided the use of SDAs. TMGN has been modified in order to have two terminal reactive silyl groups able to perform co‐condensation with a conventional organosilane (TMOS) used as a silicon source. This synthesis has allowed us to directly introduce the unmodified, functionalized TMGN as part of the walls of the mesoporous silica by a one‐pot synthesis. TMGN/SiO 2 hybrid materials present excellent catalytic properties for C–C bond forming reactions: Knoevenagel, Henry (nitroaldol), and Claisen–Schmidt condensations. The activity of the hybrid materials is higher than that of the counterpart homogeneous catalyst.