Remote Activation of Disarmed Thioglycosides in Latent-Active Glycosylation via Interrupted Pummerer Reaction
Remote Activation of Disarmed Thioglycosides in Latent-Active Glycosylation via Interrupted Pummerer Reaction
复制标题
通过中断的 Pummerer 反应远程激活潜在活性糖基化中解除武装的硫代糖苷
DOI：
10.1021/jacs.6b08305
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发表时间：
2016
影响因子：
15
通讯作者：
Wan Q.
中科院分区：
文献类型：
--
作者：
Xiao X.;Zhao Y.;Shu P.;Zhao X.;Liu Y.;Sun J.;Zhang Q.;Zeng J.;Wan Q.
通过简单和选择性氧化，S-糖苷，S-2-(2-丙硫基)苄基(SPTB)糖苷被转化为相应的氧化糖基供体，S-2-(2-丙硫酰基)苄基(SPSB)糖苷。用三氟甲磺酸酐处理解除武装的 SPSB 供体和各种受体，以良好至优异的收率提供了所需的糖苷。同时，对硫代亚磺酸盐、硫代磺酸盐和二硫化物的观察表明，离去基团是通过中断的普默勒反应被激活的。解除武装的SPSB硫糖基供体可以在各种硫糖苷存在下通过远程激活模式选择性激活。最后，利用这种新开发的方法，以收敛方式有效合成了两种天然保肝苷，狮子子草苷E和狮子子草苷B。
S-glycosides,S-2-(2-propylthio)benzyl (SPTB) glycosides, were converted to the corresponding oxidized glycosyl donors,S-2-(2-propylsulfinyl)benzyl (SPSB) glycosides, by simple and selective oxidation. Treatment of disarmed SPSB donor and various acceptors with triflic anhydride provided the desired glycosides in good to excellent yields. Meanwhile, observation of thiosulfinate, thiosulfonate, and disulfide suggested that the leaving group was activated via an interrupted Pummerer reaction. The disarmed SPSB thioglycosyl donors could be selectively activated in the presence of various thioglycosides with remote activation mode. Finally, two natural hepatoprotective glycosides, Leonoside E and Leonuriside B, were efficiently synthesized in a convergent manner with this newly developed method.