Paul Somak, Jayaraman Narayanaswamy
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, India.
Carbohydr Res. 2004 Sep 13;339(13):2197-204. doi: 10.1016/j.carres.2004.07.010.
Synthesis of 2-deoxy-1-thioglycosides from glycals, mediated by catalytic amounts of ceric ammonium nitrate is reported. Apart from the 2-deoxy-1-thioglycosides, formation of the 2,3-unsaturated enose, corresponding to the Ferrier product, is also observed, especially for the glucal substrates. A radical oxocarbenium ion and a thiolate intermediates are most likely to mediate the reaction. Upon synthesis of 2-deoxy-1-thioglycosides, few representative glycosylation reactions with both aglycosyl and glycosyl acceptors were performed and alpha-anomeric 2-deoxy glycosides were obtained exclusively.
据报道，在催化量的硝酸铈铵介导下，由糖烯合成2-脱氧-1-硫代糖苷。除了2-脱氧-1-硫代糖苷外，还观察到对应于费里尔产物的2,3-不饱和烯糖的形成，尤其是对于葡萄糖烯底物。自由基氧鎓离子和硫醇盐中间体最有可能介导该反应。在合成2-脱氧-1-硫代糖苷后，进行了一些与糖苷配基和糖苷受体的代表性糖基化反应，并且仅获得了α-异头物2-脱氧糖苷。
