2-Deoxy-3-C-(hydroxymethyl)-D-pentofuranose Derivatives: Stereoselective Synthesis and Conversion into a Novel Class of Nucleoside Analogues

Article abstract of DOI:10.1021/jo00127a041

Oxidation of pure anomers of 5-O-monoprotected methyl 2-deoxy-D-ribofuranosides 3-6 followed by Lombardo methylenation afforded the novel 3-C-methylene pentofuranosides 11 - 14.Subsequent osmium tetraoxide-catalyzed dihydroxylations of 11, 13, and 14 afforded a mixture of erythro- and threo-configured 3-C-hydroxymethyl furanosides 15/16, 18/19, and 20/21, respectively.However, analogous dihydroxylation of 5-O-(4-phenylbenzoyl)-protected β-anomer 12 proceeded with complete stereoselectivity to give 3-C-(hydroxymethyl)-β-D-erythro pentofuranoside 17 in 76percent yield.Conversion of 17 to the corresponding primary tosylate 22, followed by base-catalyzed nucleophilic attack by the nucleobases adenine and thymine, afforded after deprotection compounds 25 and 26, respectively, as the first examples of a novel class of nucleoside analogues.