Commercial Silica Materials Functionalized with a Versatile Organocatalyst for the Catalysis Of Acylation Reactions in Liquid Media

Abstract

Silica materials, natural and synthetic variants, represent a promising material for the application in heterogeneous organocatalysis due to their readily modifiable surface and chemical inertness. To achieve high catalyst loadings, usually, porous carriers with high surface areas are used, such as silica monoliths or spherical particles for packed bed reactors. While these commercial materials were shown to be efficient supports, their synthesis is elaborate, and thus less complex and cheaper alternatives are of interest, especially considering scaling up for potential applications. In this work, two commercial silica materials functionalized with the organocatalyst 4-(dimethylamino)pyridine (DMAP) were used in catalytic acylation reactions: a mesoporous silica gel (Siliabond-DMAP) and non-porous silica nanoparticles (Ludox). While both were successfully used in the acylation of phenylethanol, the latter required significantly longer reaction times, presumably due to the lack of mesopores and the associated spatial confinement, as well as agglomeration that limits the active amount of catalyst. Furthermore, we find that the influence of the linker molecule is negligible, since for two different linker motifs the reaction yields and activation energy remain largely similar. Lastly, as main result the commercial material Siliabond-DMAP, despite the non-uniform particles, were employed in a flow setup, thus demonstrating the potential as support material for application in heterogeneous organocatalysis.