Methanol-Driven Oxidative Rearrangement of Biogenic Furans – Enzyme Cascades vs. Photobiocatalysis

Abstract

The oxidative ring expansion of bio-derived furfuryl alcohols to densely functionalized six-membered O-heterocycles represents an attractive strategy in the growing network of valorization routes to synthetic building blocks out of the lignocellulosic biorefinery feed. In this study, two scenarios for the biocatalytic Achmatowicz-type rearrangement using methanol as terminal sacrificial reagent have been evaluated, comparing multienzymatic cascade designs with a photo-bio-coupled activation pathway.

(Chemo)biocatalytic Upgrading of Biobased Furanic Platforms to Chemicals, Fuels, and Materials: A Comprehensive Review

“…The desired pyranones were furnished with 31–82% isolated yields. Recently, the same group reported methanol-driven protocols using Pp AO/formaldehyde dismutase or white light/a water-soluble photocatalyst sodium anthraquinone-2-sulfonate for the enzymatic Achmatowicz reaction …”

“…Recently, the same group reported methanoldriven protocols using PpAO/formaldehyde dismutase or white light/a water-soluble photocatalyst sodium anthraquinone-2sulfonate for the enzymatic Achmatowicz reaction. 176 Subsequently, the same group developed a chemoenzymatic route to convert sterically biased FALs to pyranones, on the basis of lipase-catalyzed in situ generation of peracetic acid (Scheme 14C). 27,177 A group of pyranones were afforded in EtOAc in the presence of immobilized CAL-B and H 2 O 2 , with 51−82% yields.…”

Peroxidase-induced C–N bond formation via nitroso ene and Diels–Alder reactions

“…The combination of a peroxidase and glucose oxidase renders a highly effective dehydrogenation system that utilizes only glucose and air as stoichiometric sacrificial reagents. 15 The extensive study covers insights into the method development, the substrate scope of both intra- and intermolecular ene-type and Diels–Alder reactions, upscaling, as well as catalyst recycling.…”