Unusual reactions mediated by FMN-dependent ene- and nitro-reductases

Abstract

Due to the chemical versatility of the flavin cofactor, FMN-dependent ene-reductases and nitroreductases can catalyze or mediate a diverse spectrum of chemical reactions. Among them, two-electron transfer reactions dominate, which may proceed via sequential hydride transfer at the same or at alternate reactive sites. In addition, highly reactive intermediates are often formed, which undergo subsequent spontaneous (non-enzymatic) reactions leading to further enzymatic transformations in a cascade. Besides the well-known reductive processes involving alkenes and nitro groups at the expense of a reduced flavin cofactor, redox-neutral processes including disproportionation and CvC-bond isomerization reactions are catalyzed by OYE homologues. Unusual flavin-dependent biotransformations are reviewed with a special focus on the OYE family of flavoproteins (ene-reductases) and oxygen-insensitive FMN-dependent nitro-reductases.

The Nitro to Carbonyl Conversion (Nef Reaction): New Perspectives for a Classical Transformation

“…[103,104] Theu tilization of reductase enzymes hasb een recently reported for the Nef reaction, although the yield of the carbonylc ompounds obtained is,a tt he moment, rather modest. [105] As eries of flavin-dependent reductases has been tested using NADH or NADPH as reducing agents on different primary ands econdary nitroalkanes. [106] Under these conditions,s econdary nitroalkanes gave the corresponding ketones in am aximum yield of 17%, while reactionwith 1-nitroheptane was totally ineffective.…”

Old Yellow Enzyme-Catalysed Asymmetric Hydrogenation: Linking Family Roots with Improved Catalysis

“…Catalysts 2017, 7, 130 2 of 24 activated alkenes with an electron withdrawing group (EWG) such as aldehyde, ketone, anhydride [8,10,11], nitro [9,12,13], (di)ester [8,[14][15][16][17], (di)carboxylic acid [18][19][20], cyclic imide [21][22][23], nitrile [24], β-cyanoacrylate [25], β-nitroacrylate [26], and several other functional groups [27]. There are many examples of the high industrial potential of OYEs for the synthesis of valuable target products [28][29][30][31].…”

Broadening the Scope of Biocatalysis in Sustainable Organic Synthesis

“…[116] Protein engineering strategies have been successfully employed to broaden the substrate scope and improve/invertt he stereoselectivities of EREDs. [117] Flavin-dependent EREDS and the related nitroreductases have been shown [118] to catalyzeavariety of reactions including double bond isomerizations.…”