UC Davis

5-(Chloromethyl)furfural (CMF) is a versatile, biobased platform molecule that can be made in high yield directly from raw biomass. Although many studies have been dedicated to the applications of CMF, carbon nucleophilicity in CMF-derived molecules remains little explored. This work describes several strategies to prepare and utilize CMF-derived carbon nucleophiles based on the furylogous effect. Biobased 5-(chloromethyl)furoate and 5-methylfuroate esters were directly deprotonated to function as furylogous enolates. The chloromethylfuroates can also participate in Reformatsky-type reactions, giving carbonyl addition products in high yields. This study was extended to furylogous malonate esters, which react well with aromatic aldehydes under Knoevenagel conditions. Biobased synthetic colorants were developed in moderate to excellent yields covering a spectrum from yellow to red. Through the study and discussion of furylogous enolate chemistry, this work describes continuing efforts to develop practical tools in the synthetic repertoire for converting cellulosic biomass into useful organic molecules.