Utilization of bio-based glycolaldehyde aqueous solution in organic synthesis: application to the synthesis of 2,3-dihydrofurans

Jing Xu (1) , Wenbo Huang (1) , Rongxiang Bai (1) , Yves Queneau (2) , François Jerome (3) , Yanlong Gu (1)

1 HUST - Huazhong University of Science and Technology [Wuhan]
2 COB - Chimie Organique et Bioorganique
3 IC2MP [Poitiers] - Institut de chimie des milieux et matériaux de Poitiers [UMR 7285]

Glycolaldehyde is a biomass-derived chemical compound available from cellulose or glucose. Until now, little attention has been devoted to its use towards value-added chemicals. To explore novel transformations of glycolaldehyde, in this work, a three-component reaction of glycolaldehyde, indole and a 1,3-dicarbonyl compound was developed to synthesize a class of 3-(indol-3-yl)-2,3-dihydrofurans. Using glycolaldehyde diethyl acetal as a glycolaldehyde source, the reaction can be performed in organic solvents, and two catalytic systems were proved to be effective: (a) Sc(OTf) 3 /nitromethane and (b) Ni(ClO 4) 2 ·6H 2 O/ acetonitrile. However, these conditions applied to the direct use of the bio-based glycolaldehyde aqueous solution did not provide the dihydrofurans efficiently. To enable the use of an aqueous solution of glycolaldehyde, a hitherto unreported deep eutectic solvent (DES) was developed by using FeCl 3 ·6H 2 O and meglumine (N-methylglucamine) as precursors. The FeCl 3 ·6H 2 O/meglumine DES was characterized by FTIR, TGA and DSC, and the obtained results demonstrated unambiguously the formation of a DES. This DES was found to be an efficient and water-compatible promoting medium for the abovementioned three-component reaction. A variety of 3-(indol-3-yl)-2,3-dihydrofurans were synthesized in good yields. The FeCl 3 ·6H 2 O/meglumine DES system can also be recycled without significant loss of activity.

Domains: Organic chemistry

Jing Xu, Wenbo Huang, Rongxiang Bai, Yves Queneau, François Jerome, et al.. Utilization of bio-based glycolaldehyde aqueous solution in organic synthesis: application to the synthesis of 2,3-dihydrofurans. Green Chemistry, 2019, 21 (8), pp.2061-2069. ⟨10.1039/C8GC04000A⟩. ⟨hal-02884791⟩