Studies on the synthesis and unusual behavior of vinyl sulfone-modified hexenopyranosylthymines.
Although vinyl sulfone-modified- (VSM) pent-2'-enofuranosyl nucleosides 2 and hex-2-enopyranosyl glycoside 4 are easily synthesized from the corresponding mesylated sulfones 1c and 3c, respectively, via an oxidation-mesylation-elimination route, the 3'-C-sulfonyl-hex-2'-enopyranosylthymine 11 is not obtained from 10 and a glycal derivative 12 is formed instead. On the other hand, 3'-C-sulfonyl-hex-3'-enopyranosylthymine 20 is easily synthesized from the mesylated sulfone 19. Again unlike the reaction patterns of VSM-pent-2'-enofuranosyl nucleosides 2 and hex-2-enopyranosyl glycosides 4 as Michael acceptors, the reactions of nucleophiles with 3'-C-sulfonyl-hex-3'-enopyranosylthymine 20 yielded a rearranged product 21 instead of Michael adducts.
Deshpande
Sachin G
SG
Organic Chemistry Division (Synthesis), National Chemical Laboratory, Pune 411 008, India.
Suresh
Cheravakkattu G
CG
Pathak
Tanmaya
T
D015394:Molecular Structure; D013450:Sulfones / Q000737:chemistry*; D013936:Thymidine / Q000031:analogs & derivatives* / Q000138:chemical synthesis
D013450:Sulfones; C009873:divinyl sulfone; D013936:Thymidine