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Hierarchically porous monolithic silica shows promise as a carrier material for immobilized organocatalysts. Conventional analysis usually includes physisorption, infrared spectroscopy and elemental analysis, among others, to elucidate the pore space and degree of functionalization of the material. However, these methods do not yield information about the spatial distribution of the organic species inside the monolithic reactor. In this work, time‐of‐flight secondary ion mass spectrometry has been applied to characterize the surface of organically functionalized silica monoliths. Cross sections of a silica monolith functionalized with 4‐dimethylaminopyridine were analyzed and the results were compared with physisorption and elemental analysis experiments of the same material. This way, insight into the radial distribution of the catalyst could be achieved, which might assist in interpreting the performance of such reactors in heterogeneous flow catalysis. [ABSTRACT FROM AUTHOR]

Organocatalysis via the enamine mechanism developed to one of the most relevant tools in carbonyl chemistry and is widely used in asymmetric organic synthesis. In this work, a strategy is presented to conveniently immobilize a peptide‐based catalyst on silica supports for use in continuous flow catalysis reactions. A set of different porous silica supports is investigated spanning from mesoporous silica particles with defined pore sizes suitable for packed bed column reactors to silica monoliths with hierarchical meso‐macropore spaces. While the silica supports are functionalized with norbornene entities, the peptide‐based organocatalyst is modified with a tetrazine moiety, enabling the immobilization via inverse electron‐demand Diels‐Alder (IEDDA) reaction. The ligation results in catalyst loadings up to 0.2 mmol g‐1, without compromising the mesopore network. The catalytic activity of the materials is proven by the asymmetric C−C coupling reaction of n‐butanal to ß‐nitrostyrene proceeding in high yield and enantioselectivity in both batch and continuous flow setups. [ABSTRACT FROM AUTHOR]

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., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)