Diverse N-Oxidation of Primary Aromatic Amines Controlled by Engineered P450 Peroxizyme Variants Facilitated by Dual-Functional Small Molecule.

ABSTRACT: Amine oxidation is an important organic reaction for the production of high-value N-containing compounds. However, it is still challenging to control the reactivity of active N-centered radicals to selectively access N-oxidation products. Herein, this study reports the engineering of cytochrome P450BM3 into multifunctional N-oxidizing enzymes with the assistance of dual-functional small molecules (DFSM) to selectively produce N-oxygenation (i.e., p-nitrosobenzene, p-nitrobenzene, and azoxybenzene) and one-electron oxidation products (i.e., oligomeric quinones and azobenzene) from aromatic amines. The best mutant, F87A/T268V/V78T/A82T, exclusively gives p-nitrosobenzene (up to 98% selectivity), whereas the selectivity for p-nitrobenzene is >99% using the mutant F87A/T268V/A82T/I263L. Crysta

SUBMITTER: Chen J 

PROVIDER: S-EPMC11809401 | biostudies-literature | 2025 Feb

REPOSITORIES: biostudies-literature