(S)-γ-Hydroxymethyl-α,β-butenolide, a Valuable Chiral Synthon: Syntheses, Reactivity, and Applications

Abstract

Chirality is greatly sought for pharmaceutical compounds or fragrance and flavors.(S)-γ-hydroxymethyl-α,β-butenolide, aka HBO, is a chiral (5H)-furanone providing a polarized double bond, a lactone ring and a primary alcohol as playground for synthetic chemists. This molecule has been used for forty years in a wide range of synthetic pathways to natural and/or bioactive molecules. Its own synthesis, always from biosourced product, has also significantly evolved and could be now achieved both at large scale and by applying Green Chemistry principles. This review will explore the syntheses, the reactivity and the uses of HBO.

Sustainable One-Pot Synthesis and Polycondensation of a Levoglucosenone-Derived Cyclic Acetal Diol

“…1 H NMR spectra of samples were recorded at 300 MHz (CDCl 3 , CD 3 OD, DMSO-d 6 , and acetone-d 6 residual signals at 7.26, 3.31, 2.50, and 2.05 ppm, respectively). 13 C NMR spectra of samples were recorded at 75 MHz (CDCl 3 , CD 3 OD, DMSO-d 6 , and acetone-d 6 residual signals at 77.2, 49.0, 39.5, and 29.8 ppm, respectively). Chemical shifts are reported in parts per million (ppm).…”

“…9,10 The development of the Furacell technology in 2006 11 by Circa has been the cornerstone of success for Cyrene since it drastically lowered the cost to produce the key cellulosederived precursor levoglucosenone (LGO), a versatile bicyclic α,β-unsaturated ketone (Scheme 2). In addition to its potential as a chemical intermediate for the synthesis of high valueadded chemicals, 13 LGO has been recently used for the preparation of novel monomers and polymers. For instance, Saito and co-workers reported the formation of LGO-based acrylates through reduction of the ketone moiety of Cyrene followed by acrylation to form polyacrylates with desirable thermal properties.…”

Mechanochemical synthesis of (4S)-N-alkyl-4,5-bis-sulfooxypentanamideviaa one-pot sequential aminolysis-sulfation reaction of (S)-γ-hydroxymethyl-γ-butyrolactone (2H-HBO)

“…Recently, cellulose-derived levoglucosenone (LGO) 8 has been proven to be a very promising bio-based starting material for the synthesis of value-added chiral building blocks, namely ( S )-γ-hydroxymethyl-γ-butenolide (HBO) and ( S )-γ-hydroxymethyl-γ-butyrolactone (2H-HBO, 1 ), 9 that allow the production of a wide variety of molecules of interest 10 such as flavoring agents, 11 drug intermediates, 12 monomers and polymers. 13…”

A Validated 1H NMR Method for the Quantitation of 5-Hydroxymethyl-2(5H)-Furanone, a Valuable Chemical Intermediate, In a Dichloromethane Extract of Helleborus lividus subsp: Corsicus Leaves from Corsica

“…(S)-5-Hydroxymethyl-2(5H)-furanone is a versatile chemical intermediate used for the syntheses of a wide range of natural and/or bioactive compounds such as norrisolide, trans-burseran, or steganacin [1][2][3]. Its reactivity, applications, and its own syntheses have been extensively investigated for forty years and the reported results have been recently reviewed by Flourat et al [4]. Synthetic pathways leading to (S)-5-hydroxymethyl-2(5H)-furanone have signi cantly evolved since the end of the 70's and could be now achieved by applying green chemistry principles [4].…”

“…Its reactivity, applications, and its own syntheses have been extensively investigated for forty years and the reported results have been recently reviewed by Flourat et al [4]. Synthetic pathways leading to (S)-5-hydroxymethyl-2(5H)-furanone have signi cantly evolved since the end of the 70's and could be now achieved by applying green chemistry principles [4]. is molecule, rarely found as a natural compound, was reported for the rst time, at very low content, in a Clematis hirsuta (Ranunculaceae) butanol extract after puri cation [5].…”