Chloroperoxidase‐Catalyzed Achmatowicz Rearrangements. Issue 20 (6th May 2018)

• Record Type: Journal Article
• Authors: Thiel, Daniel; Blume, Fabian; Jäger, Christina; Deska, Jan
• Is Part Of: European journal of organic chemistry. Issue 20/21(2018)
• Page Start: 2717
• Page End: 2725
• Publication Date: 2018-05-06
• Subjects: Enzyme catalysis -- Peroxidases -- Ring expansion -- Heterocycles -- Furan; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201800333
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Chloroperoxidase from Caldariomyces fumago catalyzes the selective oxidation of furfuryl alcohols in an Achmatowicz‐type ring expansion. In combination with glucose oxidase as oxygen‐activating biocatalyst, a purely enzymatic, aerobic protocol for the synthesis of 6‐hydroxypyranone building blocks is obtained. Thanks to an only modest stereochemical bias of the oxygenating heme protein, optically active alcohols of either configuration are converted without a significant mismatch opening up opportunities for enantioselective multienzymatic cascades. Balancing the oxidase‐driven aerobic activation, extended enzyme half‐lives and productive conversion of poorly soluble and slowly reacting substrates can be achieved with high yields of the six‐membered O‐heterocycles. Abstract : Chloroperoxidase from Caldariomyces fumago catalyzes the selective oxidation of a variety of functionalized furfuryl alcohols in an Achmatowicz‐type ring expansion. In combination with glucose oxidase as oxygen‐activating biocatalyst, a purely enzymatic, aerobic protocol for the synthesis of 6‐hydroxypyranone building blocks is obtained.