Journal of Organic Chemistry 2009-03-20

Additive Pummerer reaction of 3,5-O-(di-tert-butyl)silylene-4-thiofuranoid glycal: a high-yield and beta-selective entry to 4'-thioribonucleosides.

Kazuhiro Haraguchi, Hiromitsu Matsui, Shin Takami, Hiromichi Tanaka

Index: J. Org. Chem. 74(6) , 2616-9, (2009)

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Abstract

Upon reacting 3,5-O-(di-tert-butyl)silylene-4-thiofuranoid glycal S-oxide (6) with Ac(2)O/TMSOAc/BF(3) x OEt(2) in CH(2)Cl(2), the additive Pummerer reaction proceeded to furnish the corresponding 1,2-di-O-acetyl-4-thioribofuranose 7. Compound 7 serves as a highly beta-selective glycosyl donor in the Vorbruggen condensation carried out in the presence of TMSOTf. Thus, the 4-thio-beta-D-ribofuranosyl derivatives of uracil, thymine, N (4) -acetylcytosine, 6-chloropurine, and 2-amino-6-chloropurine were synthesized. The use of 7 can be extended to the beta-selective synthesis of 4'-thio-C-ribonucleosides.