Organic solvent- and catalyst-free Baeyer–Villiger oxidation of levoglucosenone and dihydrolevoglucosenone (Cyrene®): a sustainable route to (S)-γ-hydroxymethyl-α,β-butenolide and (S)-γ-hydroxymethyl-γ-butyrolactone

Abstract

Aqueous H2O2-mediated Baeyer–Villiger oxidation of levoglucosenone provides valuable chiral lactone HBO in one step without an organic solvent, catalyst nor acid.

Chemo-Enzymatic Synthesis and Free Radical Polymerization of Renewable Acrylate Monomers from Cellulose-Based Lactones

“…10 The first route involved a lipase-mediated Baeyer-Villiger oxidation of LGO 11 whereas the more recent route is a solvent-free and catalyst-free Baeyer-Villiger oxidation. 12 The versatility of HBO has been employed to access not only valuable chiral building blocks such as chiral epoxides, but also end products such as enantiopure (S)-dairy lactone 13 employed as a butter-like flavoring agent in food sectors such as the snack, ice cream, and bakery industries.…”

Sustainable Synthesis and Polycondensation of Levoglucosenone‐Cyrene‐Based Bicyclic Diol Monomer: Access to Renewable Polyesters

“…Over the last decades, several processes that involve either chemical or chemoenzymatic conditions have been proposed to synthesize HBO from LGO by Baeyer–Villiger oxidations. For example, in 2018 we reported the organic‐solvent‐free oxidation of LGO into HBO with 30 % aqueous H 2 O 2 without any catalyst (Scheme ). Besides its attractiveness as a precursor for the synthesis of such a bio‐based acrylate, HBO could also be transformed into an AB‐ or AA′‐type monomer if another alcohol or acid function could be added to its structure.…”

“…To the best of our knowledge, no further optimizations or chemical transformations were performed to take advantage of this promising molecule that offers a playground for chemists because of its two ketone moieties. By building on our experience with LGO upgrading through sustainable synthetic processes, we investigated the implementation of the aforementioned Baeyer–Villiger‐based strategy to LGO‐Cyrene TM to access the corresponding 2H‐HBO‐HBO as a new bio‐based AA′‐type diol monomer with the aim to produce renewable polyesters with the HBO motif (Scheme ).…”

Bio‐available Solvent Cyrene: Synthesis, Derivatization, and Applications

“…[31] Furthermore, treatment of Cyrene with aqueous hydrogen peroxide afforded the unsaturated chiral lactone (S)-g-hydroxymethyl-a,b-butyrolactone (4)i ng ood yield (Scheme1b). [32] The Beckmann rearrangemento fC yrened erivatives can give av ariety of products depending on the specific conditions that are employed. Valeev et al treatedt he oxime derivativeo f Cyrene (2)w ith thionyl chloride to afford chloro nitrile 5 as a single enantiomer in good overall yield (Scheme 2a).…”