Catalytic properties of dendron–OMS hybrids

Abstract

The synthesis and catalytic testing of several dendron–ordered mesoporous silica hybrids are reported. These materials are active in both the nitroaldol (Henry) reaction and the transesterification of glyceryl tributyrate to afford methyl esters. In both reactions it is observed that dendrons terminated with primary amines are more catalytically active than samples containing dendrons terminated with secondary amines. On a mmol nitrogen per gram of silica basis, the first generation dendrons are the most active for both chemistries, and the SBA-15 samples display a higher activity than the MCM-41 samples. The pore-size effect observed is consistent with significant diffusion resistance in the MCM-41 samples. The activity trend observed in the SBA-15 materials is consistent with decreased cooperative effects between the amines and surface silanols as the dendrons become larger. Clear trends are observed indicating that higher generation dendrons are more selective to alcohol formation in the Henry reaction. The dendron catalysts are much more active and stable than simple amines attached to silica in the transesterification of triglycerides. Preliminary results shown indicate that these materials can also catalyze more demanding chemistries, an example of which is the Aldol condensation of 5-(hydroxymethyl)furfural and acetone. The results shown indicate that dendron–OMS hybrids can serve as effective solid base catalysts for a diverse range of chemistries.