Biobased 5-(chloromethyl)furoate and 5-methylfuroate esters can be deprotonated to function as furylogous lithium enolates, and the former can also undergo zinc insertion to access Reformatsky-type chemistry. Carbon nucleophilicity represents hitherto little-explored reactivity in these key carbohydratederived platform molecules, expanding their synthetic utility and potentially opening up new sustainable product markets (e. g., in epoxy resins or biobased dyes).

5-(Chloromethyl)furfural (CMF) is a cellulose derivative of increasing appeal as a renewable platform molecule. Although its role as an electrophile has been broadly studied, little is known about its potential utility as a carbon nucleophile. This work describes the preparation of organozinc reagents based on CMF by the insertion of zinc metal into the C−Cl bond. Reformatsky-type reactions are observed with a range of electrophiles under mild conditions in good to high yields. A kinetic study of zinc insertion shows the generation of this organometallic reagent from renewable furoate esters is a facile process. This method constitutes a practical tool in the synthetic repertory for the conversion of cellulosic biomass into useful organic molecules.

How well does the undergraduate organic chemistry laboratory curriculum prepare students for academic research, or for a bench job in industry? Running experiments that are more representative of research chemistry has the potential to better equip students for working in a research laboratory, while at the same time giving them insight into a typical outcome in a research project. We describe here an experiment that we have launched in the sophomore organic chemistry lab at UC Davis that presents challenges in chromatographic separation, structural assignment by NMR, and mechanistic interpretation. Optional exercises in computational modeling of the NMR data and chromophore analysis by UV–vis/fluorescence measurements are included.

The 5‐(chloromethyl)furfural (CMF) derivative ethyl 5‐(chloromethyl)furan‐2‐carboxylate undergoes two‐electron electrochemical reduction in a simple, undivided cell to give the corresponding furylogous enolate anion, which can either be quenched with carbon dioxide to give a 5‐(carboxymethyl)furan‐2‐carboxylate or with hydrogen ion to give a 5‐methylfuran‐2‐carboxylate, thereby expanding the derivative scope of CMF as a biobased platform molecule.

The chemistry of furylogous malonic and cyanoacetic esters prepared from 5-(chloromethyl)furfural (CMF), a highly versatile biobased platform molecule, was investigated. Hydrogen isotope exchange data and computational results show a significant degree of remote methylene activation by the furylogy effect. The installation of strong chromophores using Knoevenagel chemistry with natural aldehydes leads to a series of biobased synthetic colorants in good to excellent yields. Fabric dyeing tests showed their potential to serve as alternatives to petrochemical dyes in the textile industry.