A Synthetic Strategy for Saxitoxin Skeleton by a Cascade Bromocyclization: Total Synthesis of (+)-Decarbamoyl-α-saxitoxinol.
A Synthetic Strategy for Saxitoxin Skeleton by a Cascade Bromocyclization: Total Synthesis of (+)-Decarbamoyl-α-saxitoxinol.
复制标题
通过级联溴环化合成石房蛤毒素骨架的策略：(+)-Decarbamoyl-α-石房蛤毒素醇的全合成。
DOI：
10.1021/acs.orglett.6b03262
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发表时间：
2016
期刊：
影响因子：
5.2
通讯作者：
T.
中科院分区：
文献类型：
--
作者：
Ueno;S.; Nakazaki;A.; Nishikawa;T.
提出了一种新的合成石房蛤毒素ABC三环骨架的方法。BC环部分，包括aspiro-aminal结构，首先通过新设计的级联溴环化的容易获得的内部炔轴承胍和脲立体选择性地构建。然后通过环脲的鸟苷酰化合成A环，环脲通过级联产物的二醇的氧化裂解容易地制备，然后加入氰化物。该策略使得（+）-十氨甲酰基-α-石房蛤毒素醇（一种天然存在的石房蛤毒素类似物）的简明立体控制全合成成为可能。
A new synthetic strategy for the formation of the ABC tricyclic framework of saxitoxin was developed. The BC ring moiety, including aspiro-aminal structure, was first constructed stereoselectively by a newly designed cascade bromocyclization of a readily available internal alkyne bearing guanidine and urea. The A ring was then synthesized by a guanylation of a cyclic urea, easily prepared via the oxidative cleavage of the diol of the cascade product, followed by addition of cyanide. This strategy enables the concise stereocontrolled total synthesis of (+)-decarbamoyl-α-saxitoxinol, which is a naturally occurring saxitoxin analogue.