TY - JOUR

T1 - Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran

T2 - Organic synthesis based on biomass-derived products

AU - Ryabukhin, Dmitry S.

AU - Zakusilo, Dmitry N.

AU - Kompanets, Mikhail O.

AU - Tarakanov, Anton A.

AU - Boyarskaya, Irina A.

AU - Artamonova, Tatiana O.

AU - Khohodorkovskiy, Mikhail A.

AU - Opeida, Iosyp O.

AU - Vasilyev, Aleksander V.

N1 - Publisher Copyright: © 2016 Ryabukhin et al.; licensee Beilstein-Institut. Copyright: Copyright 2016 Elsevier B.V., All rights reserved.

PY - 2016/10/5

Y1 - 2016/10/5

N2 - The reaction of 5-hydroxymethylfurfural (5-HMF) with arenes in superacidic trifluoromethanesulfonic acid (triflic acid, TfOH) as the solvent at room temperature for 1-24 h gives rise to 5-arylmethylfurfurals (yields of 17-91%) and 2-arylmethyl-5-(diarylmethyl) furans (yields of 10-37%). The formation of these two types of reaction products depends on the nucleophilicity of the arene. The same reactions under the action of acidic zeolites H-USY in high pressure tubes at 130 °C for 1 h result in the formation of only 5-arylmethylfurfurals (yields of 45-79%). 2,5-Diformylfuran (2,5-DFF) in the reaction with arenes under the action of AlBr3 at room temperature for 1 h leads to 5-(diarylmethyl)furfurals (yields of 51-90%). The reactive protonated species of 5-HMF and 2,5-DFF were characterized by NMR spectroscopy in TfOH and studied by DFT calculations. These reactions show possibilities of organic synthesis based on biomass-derived 5-HMF and 2,5-DFF.

AB - The reaction of 5-hydroxymethylfurfural (5-HMF) with arenes in superacidic trifluoromethanesulfonic acid (triflic acid, TfOH) as the solvent at room temperature for 1-24 h gives rise to 5-arylmethylfurfurals (yields of 17-91%) and 2-arylmethyl-5-(diarylmethyl) furans (yields of 10-37%). The formation of these two types of reaction products depends on the nucleophilicity of the arene. The same reactions under the action of acidic zeolites H-USY in high pressure tubes at 130 °C for 1 h result in the formation of only 5-arylmethylfurfurals (yields of 45-79%). 2,5-Diformylfuran (2,5-DFF) in the reaction with arenes under the action of AlBr3 at room temperature for 1 h leads to 5-(diarylmethyl)furfurals (yields of 51-90%). The reactive protonated species of 5-HMF and 2,5-DFF were characterized by NMR spectroscopy in TfOH and studied by DFT calculations. These reactions show possibilities of organic synthesis based on biomass-derived 5-HMF and 2,5-DFF.

KW - 2,5-diformylfuran

KW - 5-hydroxymethylfurfural

KW - Friedel-Crafts reaction

KW - Superacids

KW - Zeolites

UR - http://www.scopus.com/inward/record.url?scp=84992061308&partnerID=8YFLogxK

U2 - 10.3762/bjoc.12.202

DO - 10.3762/bjoc.12.202

M3 - Article

VL - 12

SP - 2125

EP - 2135

JO - Beilstein Journal of Organic Chemistry

JF - Beilstein Journal of Organic Chemistry

SN - 1860-5397

ER -