Diversification of the Renewable Furanic Platform via 5‐(Chloromethyl)furfural‐Based Carbon Nucleophiles

Abstract

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).

Furylogous Nucleophile Chemistry for the Preparation of Renewable Dyes

“…reactivity, whereas the simple enolate of the dehalogenated furoate participated in classic carbon nucleophile reactions such as alkylation and addition to carbonyl compounds. 12 On the other hand, metalation of the halide led to Reformatskytype reactivity with a range of aldehydes. 14 In recent work, we have described the electrochemical fixation of the greenhouse gas carbon dioxide into ethyl 5-(chloromethyl)furan-2-carboxylate 2 to give, after esterification, ethyl 5-(carbethoxymethyl)furan-2-carboxylate 3.…”

“…To establish a context for the reactivity we are advancing, Figure shows the natural charge affinity of a 5-(chloromethyl)­furoate ester, which can be derived from CMF by oxidation with a simple reagent mixture consisting of household bleach, acetic acid, and tert -butanol followed by esterification with the relevant alcohol . Thus, deprotonation of the furoate ester was observed to lead to Darzens-type reactivity, whereas the simple enolate of the dehalogenated furoate participated in classic carbon nucleophile reactions such as alkylation and addition to carbonyl compounds . On the other hand, metalation of the halide led to Reformatsky-type reactivity with a range of aldehydes …”

“…1 CMF 1 is a highly versatile biobased platform chemical and disruptive innovation in the field of biorefinery research. 10,11 Here, we further develop the concept of furylogy, 12…”

“…In our previous work, a butenolide from biomass-derived levulinic acid was condensed with a derivative of 5-(chloromethyl)­furfural (CMF) 1 to give chromophores that showed excellent performance as dyes. 1 CMF 1 is a highly versatile biobased platform chemical and disruptive innovation in the field of biorefinery research. , Here, we further develop the concept of furylogy, by which we have been able to expand the scope of colorant chemistry that stems from CMF.…”

Generation of Organozinc Nucleophiles Based on the Biomass-Derived Platform Molecule 5-(Chloromethyl)furfural

“…Recently, we communicated the applications of furylogous enolate chemistry to the extension of the six-carbon framework of CMF to C 7 , C 11 , C 12 , C 18 , and C 22 systems, mainly for the purposes of generating extended chromophores for biobased dye production . We now report in full on the production of organozinc nucleophiles from CMF-derived esters in terms of insertion kinetics, solvent and temperature effects, and electrophile scope.…”