Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

Abstract

Although different ways of converting 5-(hydroxymethyl)furfural (1) to various substrates with high value have been sought, few transformations have obtained building blocks that can be very useful in the area of fine chemistry. Herein, we report the synthesis of protoanemonin (5-methylenefuran-2(5H)-one) from D-fructose via compound (1), a versatile γ-alkylidenebutenolide, using an efficient selfcatalysed process with formic acid, with high reaction performance and selectivity (up to 94% yield and 98% conversion from (1), while 28% yield from D-fructose). This efficient and simple operational process involved a two-phase aqueous-organic system between chlorinated solvents (CH x Cl y) and hydrogen peroxide as the initial oxidizing agent. The reaction presents a key cleavage in the 5-hydroxymethyl moiety of (1), due to the Baeyer-Villiger oxidation (BVO) process that generates formic acid in situ. Ultimately, DFF and HMF were successfully obtained in 80% and 98% yield, respectively, starting from D-fructose and using Preyssler heteropolyacids as Brønsted acid catalysts under an atmosphere of oxygen in the absence of hydrogen peroxide.

Two-photon-absorbing ruthenium complexes enable near infrared light-driven photocatalysis

“…The most common product from HMF oxidation is either 2,5-furandicarboxylic acid [58][59][60] or 2,5-diformylfuran 61,62 , both of which are valuable polymer precursors. In contrast, O 2 -initiated HMF oxidation can result in other value-added fine chemicals, such as maleic acid anhydride (MA) and 5-hydroxy-4-keto-2pentenoic acid (HKPA), but these reactions remain underexplored 63,64 . Herein, we demonstrate that using 5 as the photosensitizer, NIR light irradiation (λ irr = 740 nm) was able to drive the transformation of HMF to MA (55% yield) and HKPA (37% yield) in the presence of O 2 with an overall HMF conversion of 92% within 5 h (Fig.…”

Baeyer–Villiger oxidation: a promising tool for the synthesis of natural products: a review

“…In 2020, Martinez and companions reported the 1st one-pot selective synthesis of g-alkylidenebutenolide (protoanemonin) in overall 25% yield from D-fructose 176 through 5-(hydroxy methyl) furfural 177 by employing Baeyer-Villiger oxidation. 162 In the beginning, D-fructose 176 was converted into 5-(hydroxy methyl) furfural 177 in 98% yield in the presence of hypophosphorous acid (HPA). Homogenous Darunavir 2 is a potent natural drug which belongs to protease inhibitor therapeutics, an important part of cART (combination antiretroviral therapies) procedure.…”

“…In 2020, Martinez and companions reported the 1st one-pot selective synthesis of γ-alkylidenebutenolide (protoanemonin) in overall 25% yield from d -fructose 176 through 5-(hydroxy methyl) furfural 177 by employing Baeyer–Villiger oxidation. 162 In the beginning, d -fructose 176 was converted into 5-(hydroxy methyl) furfural 177 in 98% yield in the presence of hypophosphorous acid (HPA). Homogenous autocatalysis and H 2 O 2 -mediated-Baeyer–Villiger oxidation of compound 177 in chlorinated solvent afforded the protoanemonin 179 in 94% yield from 177 and 28% yield from 176 ( Scheme 24 ).…”

B-Containing Hydrotalcites Effectively Catalyzed Synthesis of 3-(Furan-2-yl)acrylonitrile Derivatives via the Knoevenagel Condensation

“…Continuing with our interests in obtaining new HMF derivatives under mild reaction conditions, − we studied the Knoevenagel condensation of HMF by functionalizing HMF with various active methylene compounds catalyzed by hydrotalcite-type (HT) materials impregnated with boric acid under solvent-free conditions. These materials are a family of anionic clay materials known as layered double hydroxides.…”