Dried chitosan-gels as organocatalysts for the production of biomass-derived platform chemicals

Aldol condensations between sugar-derived dehydrated aldehydes (e.g. furfural) and acetone have been proposed as a route to provide useful biomass-derived chemicals. In the quest of sustainable catalytic ways for such aldol condensations, this paper assesses the use of dried chitosan-gels as naturally-immobilized, readily available and non-hazardous amino-based organocatalysts. At room temperature chitosan dried gels are not suitable catalysts for the desired reaction. However, at higher temperatures (>900 degrees C) reaction proceeds efficiently either in solvent-free systems (with addition of catalytic amounts of water) or in water. The set-up of closed reactor set-ups (thermoshakers or microwave reactions) proved highly beneficial for the reaction outcome. Furthermore, chitosan dried gels were successfully re-used for a number of cycles. An efficient catalyst drying method (either lyophilization. or scCO(2) drying) was crucial to achieve virtually full conversions in 4 h. After pertinent further process optimization, dried chitosan-gels may become very useful catalysts for their use in biomass-based reactions in biorefineries. (C) 2012 Elsevier B.V. All rights reserved.