Fatty Acid Chain Shortening by a Fungal Peroxygenase

Abstract

A recently discovered peroxygenase from the fungus Marasmius rotula (MroUPO) is able to catalyze the progressive one‐carbon shortening of medium and long‐chain mono‐ and dicarboxylic acids by itself alone, in the presence of H2O2. The mechanism, analyzed using H2 18O2, starts with an α‐oxidation catalyzed by MroUPO generating an α‐hydroxy acid, which is further oxidized by the enzyme to a reactive α‐keto intermediate whose decarboxylation yields the one‐carbon shorter fatty acid. Compared with the previously characterized peroxygenase of Agrocybe aegerita, a wider heme access channel, enabling fatty acid positioning with the carboxylic end near the heme cofactor (as seen in one of the crystal structures available) could be at the origin of the unique ability of MroUPO shortening carboxylic acid chains.

Selective Epoxidation of Fatty Acids and Fatty Acid Methyl Esters by Fungal Peroxygenases

“…One UPO from the latter fungus is produced as a recombinant protein (r Cci UPO) by Novozymes (Bagsvaerd, Denmark) (Figure S1A) . Interestingly, the recently described Mro UPO presents differences with the best studied fungal peroxygenases, such as the ability of oxidizing bulkier substrates,, the terminal hydroxylation of n ‐alkanes and the chain‐shortening of carboxylic acids . On the other hand, Cgl UPO is the fourth wild‐type described UPO, and the first isolated from an ascomycete …”

Preparative Asymmetric Synthesis of Canonical and Non‐canonical α‐amino Acids Through Formal Enantioselective Biocatalytic Amination of Carboxylic Acids

“…50% yield; Scheme 1 B). [6,8,19] Herein, we show the development of a three-step linear biocascade for the atom-efficient formal asymmetric a-amination of saturated FAs into enantiopure l-a-AAs in one-pot, on preparative scale, using mild reaction conditions, renewable feedstocks, reagents and catalysts (Scheme 2). [17] Still, many of these routes are based on petroleum-derived feedstocks such as benzenes, olefins, aldehydes or a-HAs (Scheme 2).…”

“…[17c-e,18] A direct route for a-amination of a-/ß-saturated organic/fatty acids has (so far) been restricted by efficient and selective oxy-functionalization of the poorly activated a-carbon, scalability of oxyfunctionalization reactions for preparative synthesis (in particular with O 2 as oxidant) as well as low conversion by the respective amination catalysts. [6,8,19] Herein, we show the development of a three-step linear biocascade for the atom-efficient formal asymmetric a-amination of saturated FAs into enantiopure l-a-AAs in one-pot, on preparative scale, using mild reaction conditions, renewable feedstocks, reagents and catalysts (Scheme 2).…”

Fatty acid epoxidation byCollariella virescensperoxygenase and heme-channel variants

“…15,16 In a similar way, E. coli expression paves the way for investigating structural-functional relationships and engineering UPOs, as recently shown 17 for the previously described 6 UPO of M. rotula that catalyzes several unique reactions. 8,[18][19][20][21][22][23] Here, we report C. virescens UPO (produced in E. coli) as a new model enzyme for epoxidation reactions. Epoxides are among the most widely used intermediates in organic synthesis as precursors to complex molecules.…”