jo060224l_si_002.cif (21.85 kB)
Substrate-Dependent Dihydroxylation of Substituted Cyclopentenes: Toward the Syntheses of Carbocyclic Sinefungin and Noraristeromycin
dataset
posted on 2006-05-26, 00:00 authored by May Xiao-Wu Jiang, Bohan Jin, Jennifer L. Gage, Alain Priour, Gordon Savela, Marvin J. MillerCarbocyclic nucleosides are of considerable interest for the development of new therapeutic agents. A
key reaction in the preparation of many such nucleoside analogues is dihydroxylation of appropriately
substituted cyclopentenes. Although often considered a routine reaction, in this paper, we report the
dramatic influence of substituents on the facial selectivity of dihydroxylations. The substituted cyclopentene
substrates are derived from acylnitroso cycloaddition reactions of cyclopentadiene, followed by N−O
reduction and efficient enzymatic resolution. The results are directly utilized in a very efficient asymmetric
synthesis of an antiviral carbocyclic nucleoside, noraristeromycin 5. Extensions toward the synthesis of
carbocyclic sinefungin 7 document the importance of realizing the substituent dependence of the
dihydroxylation reaction.