(±)-3'-Deoxyaraaristeromycin via a surprising rearrangement

Article abstract of DOI:10.1016/S0040-4039(00)73876-7

Hydrolysis of (±)-3β-acetoxy-4α-benzamido-1α-cyclopentanemethyl acetate (5) with 6 N hydrochloric acid has been found to give an amine in which the configuration at C-3 has been inverted. This conclusion was reached following conversion of the amine into (±)-3'-deoxyaraaristeromycin (8) by following a standard adenine formation process of (i) reaction with 5-amino-4,6-dichloropyrimidine, (ii) ring closure with diethoxymethyl acetate, and (iii) ammonolysis. Use of basic hydrolysis conditions with 5 led to the expected (±)-3'-deoxyaristeromycin (7).