Intraparticle diffusional versus site effects on reaction pathways in liquid-phase cross aldol reactions

Chemo- and regioselectivity in a heterogeneously catalyzed cross aldol reaction were directed by tuning the nature of the sites, textural properties, and reaction conditions. Catalysts included sulfonic acid-functionalized resins or SBA-15 with varying particle size or pore diameter, H-BEA zeolites, and Sn-BEA zeotype; conditions were 25 degrees C to 170 degrees C in organic media. Benzaldehyde and 2-butanone yielded branched (reaction at -CH2- of butanone) and linear (reaction at -CH3) addition and condensation products; and fission of the branched aldol led to -methyl styrene and acetic acid. Strong acids promoted the dehydration step, and regioselectivity originated from preferred formation of the branched aldol. Both, resins and functionalized SBA-15 materials yielded predominantly the branched condensation product, unless particle morphology or temperature moved the reaction into the diffusion-limited regime, in which case more fission products were formed, corresponding to Wheeler Type II selectivity. For H-form zeolites, fission of the branched aldol competed with dehydration of the linear aldol, possibly because weaker acidity or steric restrictions prevented dehydration of the branched aldol.