The Achmatowicz Rearrangement – Oxidative Ring Expansion of Furfuryl Alcohols

Abstract

Over the years, the oxidative ring enlargement of furfuryl alcohols, known as the Achmatowicz reaction, has been developed into a powerful and versatile synthetic tool for the preparation of 6-hydroxypyranones. This review provides a comprehensive collection of the various ways to perform Achmatowicz rearrangement reactions and explores the role of this ring-expansion process in contemporary organic synthesis. 1 Introduction 2 Classical Methods and Variants 3 Single-Electron-Transfer Oxidations 4 Metal-Catalyzed Ring Expansions 5 Photolytic Oxygenations 6 Enzymatic Transformations 7 Conclusions

Syntheses of spliceostatins and thailanstatins: a review

“…In an abortive route, the addition of allyl-Grignard to 5-methylfurfural, followed by the resolution of the racemic homoallylic alcohol with Amano lipase gave (−)-51 (Scheme 6) [16]. An Achmatowicz oxidation [29] with tert-butyl hydroperoxide catalyzed by VO(acac) 2 afforded the hemiketal 52, and the ionic reduction [22] of 52 gave the enone (−)-53. The enone transposition of 53 was effected by the addition of methyl-Grignard, followed by the oxidation with PCC.…”

Chloroperoxidase‐Catalyzed Achmatowicz Rearrangements

“…While the original procedures by Achmatowicz, and Lefebvre still relied on the use of stoichiometric oxidants such as bromine or meta ‐chloroperbenzoic acid, over the years multiple powerful variations based on e.g. metal catalysis, photoactivation and electrochemistry have been brought forward providing additional selectivities and broader applicability . In light of milder and environmentally more benign approaches towards the oxidative ring rearrangement of the furfuryl derivatives, recently the use of enzymes as biological catalyst has been brought into the focus (Scheme ).…”

Enantioselective total synthesis of decytospolide A and decytospolide B using an Achmatowicz reaction

“…8 In recent years, the Achmatowicz reaction has been utilized in the synthesis of a variety of natural products. 10,11 We have utilized this reaction in the synthesis of a number of bioactive natural products containing functionalized tetrahydropyran rings. 10,12,13 In particular, the Achmatowicz reaction of furanyl alcohol 1 (Figure 1) provides dihydropyranone hemiacetal 2 which upon reduction, typically with triethylsilane in the presence of trifluoroacetic acid (TFA) provided a variety of 2,6-disubstituted dihydropyranone derivatives 3 .…”