[3+2] Annulation of allylic silanes in acyclic stereocontrol:: Total synthesis of (9S)-dihydroerythronolide A
[3+2] Annulation of allylic silanes in acyclic stereocontrol:: Total synthesis of (9S)-dihydroerythronolide A
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DOI：
10.1021/ja034865z
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发表时间：
2003-05-21
影响因子：
15
通讯作者：
Woerpel, KA
中科院分区：
文献类型：
--
作者：
Peng, ZH;Woerpel, KA
烯丙基硅烷的[3 + 2]成环反应可用于实现无环立体控制。该方法是对映选择性全合成（9 S）-二氢阿糖胞苷A的关键步骤。关键的成环反应用于建立目标的大部分立体化学，包括两个四取代的碳立体中心。靶分子的对称性允许其断开成两个相等大小的片段，这两个片段都是由相同的成环反应产生的。使用锡（II）介导的螯合控制的α-苄氧基乙基酮的羟醛缩合反应偶联两个片段。（9 S）-二氢阿糖胞苷A的收敛全合成以29步的最长线性序列和5.4%的总产率完成。
The [3 + 2] annulation reactions of allylic silanes can be utilized to achieve acyclic stereocontrol. This method was employed as a key step in an enantioselective total synthesis of (9S)-dihydroerythronolide A. The key annulation reaction served to establish most of the stereochemistry of the target, including the two tetrasubstituted carbon stereocenters. The symmetry of the target molecule allowed it to be disconnected into two equally sized fragments, both of which were generated from the same annulation reaction. The two fragments were coupled using a tin(II)-mediated chelation-controlled aldol reaction of an α-benzyloxy ethyl ketone. This convergent total synthesis of (9S)-dihydroerythronolide A was accomplished with the longest linear sequence of 29 steps and in 5.4% overall yield.