Glucosyloxymethylfurfural (GMF): a creative renewable scaffold towards bioinspired architectures

Abstract

Glucosyloxymethylfurfural (GMF) is the glucosylated analogue of hydroxymethylfurfural (HMF), and is obtained in one step from the very available disaccharide isomaltulose. This account gives an overview on the preparation and the uses of GMF towards architectures containing a carbohydrate moiety and shows that rather elaborated targets can be synthesized from GMF in very short sequences. A special focus is made on carbon-carbon formation on the aldehyde group leading to new biobased acrylic derivatives by the Baylis-Hillman reaction.

Solvent issues in the Baylis-Hillman reaction of 5-hydroxymethyl furfural (HMF) and 5-glucosyloxymethyl furfural (GMF). Towards no-solvent conditions

“…With respect to the Morita-Baylis-Hillman reaction, we have earlier investigated its application to HMF and its corresponding glucosylated analog GMF (Figure 1), available in one step from the commercial disaccharide isomaltulose. GMF, containing the furan, glucose and aldehydic entities, is able to undergo a remarkably wide range of transformations [44][45][46][47][48][49]. Strangely, applications of HMF and GMF in the Morita-Baylis-Hillman reaction were only scarcely investigated, though this route can afford interesting hydroxyacrylates with additional hydroxylated appendages.…”

Dipolar cycloadditions of HMF-based nitrones: stepwise and multicomponent reactions, stereochemical outcome and structural scope

“…We then extended the investigation to GMF, the glucosylated analog of HMF, much less available than HMF but interesting by exhibiting a remaining polar and functional moiety. [40][41][42][43] GMF-derived N-methyl nitrone 1e yielded the corresponding carbohydrate containing isoxazolidine 14 in 69% yield and moderate 65:35 regioselectivity. The cycloaddition reaction between 1e and N,N-dimethyl acrylamide led to product 15 with higher yield of 78% and a better 78:22 regioselectivity.…”

“…39 Using TBDPS-protected HMF, nitrone 1d could also be obtained readily and in excellent yields (Table 1, entry 4). The glucosylated analog of HMF, glusosyloxymethylfurfural (GMF), [40][41][42][43] was also converted to its corresponding nitrone 1e using MeOH as solvent. With this clean, efficient, and fast protocol in hands, the subsequent cycloaddition step of the isolated nitrone was then undertaken.…”

Design and Properties of a Novel Family of Nonionic Biobased Furanic Hydroxyester and Amide Surfactants

“…Considering the known applicability of the MBH reaction to HMF and analogues in mild and clean conditions, , the scope of the reaction was extended to the design of original amphiphilic systems in order to explore their physicochemical behavior. The 5-CH 2 OH appendage in HMF offers the opportunity to modulate the polarity on the furanic building block, using either HMF itself, bearing the unsubstituted CH 2 OH group, glucosyloxymethyl furfural (GMF, prepared from isomaltulose), bearing a full glucosyl substituent, ,− or succinyl-HMF (SMF), the hemiester of HMF and succinic acid (prepared by reaction following known procedures with succinic anhydride at room temperature in the presence of DMAP in DCM), , bearing a carboxylic group. Regarding the hydrophobic side, the variability relies on the use of activated alkenes in the MBH reaction, namely, alkyl acrylates of various chain lengths, from 4 to 16 carbon atoms, or alkylacrylamides.…”