Synthesis of Saxitoxin and Its Derivatives
Synthesis of Saxitoxin and Its Derivatives
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DOI：
10.1021/acs.orglett.0c03281
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发表时间：
2020-11-06
期刊：
影响因子：
5.2
通讯作者：
Chida，Noritaka
中科院分区：
文献类型：
--
作者：
Okuyama，Yuya;Okamoto，Ryosuke;Chida，Noritaka
介绍了手性合成(+)-蛤蚌毒素及其衍生物的方法。由苹果酸衍生的烯丙基邻二醇通过序贯的Overman重排，有效地在石蜡毒素的C-5和C-6上安装了两个连续的碳氮键。双环胍单元是由在C-4上有酮羰基的无环双胍衍生物在分子内形成的。由双环胺中间体(+)-蛤蚌毒素，(+)-decarbamoyl-β-蛤蚌毒素[(+)-dc-β-蛤蚌毒素]和非天然骨架异构体(−)- isodc -蛤蚌毒素]合成。
The chiral synthesis of (+)-saxitoxin and its derivatives is described. Two consecutive carbon–nitrogen bonds at C-5 and C-6 in saxitoxin were effectively installed by the sequential Overman rearrangement of an allylic vicinal diol derived fromd-malic acid. The bicyclic guanidine unit was constructed by the intramolecular aminal formation of an acyclic bis-guanidine derivative possessing a ketone carbonyl at C-4. From the bicyclic aminal intermediate, (+)-saxitoxin, (+)-decarbamoyl-β-saxitoxinol [(+)-dc-β-saxitoxinol], and the unnatural skeletal isomer, (−)-iso-dc-saxitoxinol, were synthesized.