On how the binding cavity of AsqJ dioxygenase controls the desaturation reaction regioselectivity: a QM/MM study.

ABSTRACT: The Fe(II)/2-oxoglutarate-dependent dioxygenase AsqJ from Aspergillus nidulans catalyses two pivotal steps in the synthesis of quinolone antibiotic 4'-methoxyviridicatin, i.e., desaturation and epoxidation of a benzodiazepinedione. The previous experimental results signal that, during the desaturation reaction, hydrogen atom transfer (HAT) from the benzylic carbon atom (C10) is a more likely step to initiate the reaction than the alternative HAT from the ring moiety (C3 atom). To unravel the origins of this regioselectivity and to explain why the observed reaction is desaturation and not the "default" hydroxylation, we performed a QM/MM study on the reaction catalysed by AsqJ. Herein, we report results that complement the experimental findings and suggest that HAT at the C10 position is th

SUBMITTER: Wojdyla Z 

PROVIDER: S-EPMC6015105 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature