5-(Hydroxymethyl)furfural and 5-(glucosyloxymethyl)furfural in multicomponent reactions

Abstract Multicomponent reactions (MCRs) are attractive strategies allowing short sequences toward complex chemical architectures. Several MCRs concern the reactivity of aldehydes. Therefore, carbohydrate-derived furanic aldehydes constitute a possible family of starting materials for such atom-economical strategies. Although the use of the pentose-derived furfural in MCR approaches is well documented, the case of hydroxymethylfurfural (HMF), available in one step from hexoses, has been historically less employed due its lower availability and stability. Recent developments in HMF production have changed the deal, making it nowadays a much more available substrate for any type of chemical transformation. The purpose of this chapter is to give an overview of the reactivity of HMF and glucosyloxymethylfurfural (GMF), its glucosylated analog available from isomaltulose, in MCRs. It will review several types of reactions involving nucleophilic attacks on in situ formed imines, and some examples of cycloadditions of in situ formed dipolar intermediates. It shows the diversity of complex structures reachable in one step from these increasingly available platform molecules, including some containing a glucopyranosyl moiety when GMF is concerned.