Deshpande Sachin G, Suresh Cheravakkattu G, Pathak Tanmaya
Organic Chemistry Division (Synthesis), National Chemical Laboratory, Pune 411 008, India.
Carbohydr Res. 2008 May 19;343(7):1163-70. doi: 10.1016/j.carres.2008.02.016. Epub 2008 Feb 21.
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.
尽管乙烯砜修饰的（VSM）戊-2'-烯呋喃糖基核苷2和己-2-烯吡喃糖基糖苷4可分别通过氧化-甲磺酰化-消除路线由相应的甲磺酰化砜1c和3c轻松合成，但3'-C-磺酰基-己-2'-烯吡喃糖基胸腺嘧啶11并非由10得到，而是形成了一个糖烯衍生物12。另一方面，3'-C-磺酰基-己-3'-烯吡喃糖基胸腺嘧啶20可由甲磺酰化砜19轻松合成。同样与VSM-戊-2'-烯呋喃糖基核苷2和己-2-烯吡喃糖基糖苷4作为迈克尔受体的反应模式不同，亲核试剂与3'-C-磺酰基-己-3'-烯吡喃糖基胸腺嘧啶20的反应生成了重排产物21，而非迈克尔加成物。
