Prehydrated One-Electron Attachment to Azido-Modified Pentofuranoses: Aminyl Radical Formation, Rapid H-Atom Transfer, and Subsequent Ring Opening.

ABSTRACT: Methyl 2-azido-2-deoxy-α-d-lyxofuranoside (1a) and methyl 2-azido-2-deoxy-β-d-ribofuranoside (2) were prepared from d-xylose or d-arabinose, respectively. Employing ESR and DFT/B3LYP/6-31G* calculations, we investigated (i) aminyl radical (RNH·) formation and (ii) reaction pathways of RNH·. Prehydrated electron attachment to 1a and 2 at 77 K produced transient azide anion radical (RN₃·^-) which reacts via rapid N₂ loss at 77 K, forming nitrene anion radical (RN·^-). Rapid protonation of RN·^- at 77 K formed RNH· and ^-OH. ¹⁵N-labeled-1a confirmed this mechanism. Investigations employing in-house synthesized site-specifically deuterated derivatives of 1a (e.g., CH₃ (1b), C4 (1c), and C5 (1d)) established tha

SUBMITTER: Mudgal M 

PROVIDER: S-EPMC5488683 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature