Abstract
Highly regio‐ and stereoselective monohydroxylation of the CC bond of (+)‐7‐oxabicyclo[2.2.1]hept‐5‐en‐2‐one (8) was achieved via LiAlH4 reduction of the corresponding 5,6‐exo‐epoxy dimethyl acetal 9. The reaction gave exclusively (–)‐(1R, 2R, 4S)‐6,6‐dimethoxy‐7‐oxabicyclo[2.2.1]heptan‐2‐exo‐ol (10) which was transformed into 2,5‐anhydro‐3‐O‐benzyl‐4‐deoxy‐D‐ribo‐hexonic acid (15) and 2,5‐anhydro‐4‐deoxy‐D‐ribo‐hexonic acid (6) via ozonolysis of (–)‐(1R, 4S, 6R)‐6‐exo‐benzyloxy‐2‐{[(tert‐butyl)dimethylsilyl]oxy}‐7‐oxabicyclo[2.2.1]hept‐2‐ene (14). Cordycepin C (5) was derived from 6 and 4,5,6‐triaminopyrimidine using CsF/DMF to generate the adenine heterocycle.

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