A [2.1.0]-Fused Bicyclic Intermediate Is Produced during the Biosynthesis of Oxetane Nucleosides.

ABSTRACT: AlsB and OxsB are homologous B₁₂-dependent radical S-adenosyl-l-methionine enzymes involved in the biosynthesis of the oxetane nucleosides albucidin and oxetanocin A. Both pathways also require a second enzyme (AlsA and OxsA, respectively) to complete the biosynthesis of the oxetane ring. Herein, OxsB and AlsB are both shown to catalyze an intramolecular C-C bond formation between two sp³-hybridized carbons in 5'-phosphates of 2'-deoxyadenosine to yield corresponding phosphates of the same highly strained [2.1.0]-bicyclic species. This compound undergoes nonenzymatic decomposition; however, in the presence of OxsA or AlsA, it is instead converted to oxetanocin A aldehyde phosphate or albucidin phosphate, respectively. This completes the des

SUBMITTER: Lee YH 

PROVIDER: S-EPMC12379298 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature