Ueda Yoshihiro
Institute for Chemical Research, Kyoto University.
Yakugaku Zasshi. 2016;136(12):1631-1639. doi: 10.1248/yakushi.16-00186.
The first total syntheses of multifidosides A-C are reported. The prominent feature is an unconventional retrosynthesis based on organocatalytic site-selective acylation of unprotected glycosides at the final stage of synthesis. A notable advantage of this strategy is that it avoids the risks of undesired side reactions during the removal of the protecting groups at the final stage of total synthesis. The proposed synthetic strategy has another advantage in terms of efficient late-stage derivatization of natural products. Due to the predictability and reliability of the catalytic site-selective introduction of various functionalized acyl groups, the present synthetic strategy could provide a general synthetic route to 4-O-acylglycosides, such as phenylethanoid glycosides and ellagitannins, which are of biological interest.
报道了多裂糖苷A - C的首次全合成。其突出特点是在合成的最后阶段基于有机催化的未保护糖苷的位点选择性酰化进行非常规逆合成。该策略的一个显著优点是避免了在全合成最后阶段去除保护基时发生不期望的副反应的风险。所提出的合成策略在天然产物的高效后期衍生化方面还有另一个优势。由于催化位点选择性引入各种功能化酰基的可预测性和可靠性，目前的合成策略可以为4 - O - 酰基糖苷，如具有生物学意义的苯乙醇苷和鞣花单宁，提供一条通用的合成路线。
