Removable Silyl Group as a "Masked Proton" in Oxy-2-oxonia(azonia)-Cope Rearrangement: Applications in Stereoselective Total Synthesis of Natural Macrolides
Removable Silyl Group as a "Masked Proton" in Oxy-2-oxonia(azonia)-Cope Rearrangement: Applications in Stereoselective Total Synthesis of Natural Macrolides
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可去除的甲硅烷基作为 Oxy-2-oxonia(azonia)-Cope 重排中的“掩蔽质子”：在天然大环内酯立体选择性全合成中的应用
DOI：
10.1002/ejoc.201500654
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发表时间：
2015
影响因子：
2.8
通讯作者：
Goeke Andreas
中科院分区：
文献类型：
--
作者：
Mu Wenbo;Zou Yue;Zhou Lijun;Wang Quanrui;Goeke Andreas
在刘易斯酸存在下，三甲基硅烷基取代的β，γ-不饱和酮和醛（亚胺）进行亲核加成，生成两性离子中间体，然后进行氧-2-氧鎓（氮鎓）-科普重排，得到高烯丙基酯（酰胺）。在含TMS的2-乙烯基环烷酮的情况下，该过程导致扩环，提供10至16元内酯。将该方案应用于（R）-phoracanthropine I的全合成。
In the presence of a Lewis acid, trimethylsilyl‐substituted β,γ‐unsaturated ketones and aldehydes (imines) undergo nucleophilic addition to produce zwitterionic intermediates, followed by oxy‐2‐oxonia(azonia)‐Cope rearrangements to give homoallylic esters (amides). In the case of TMS‐containing 2‐vinylcycloalkanones, the process results in ring‐enlargement, providing 10‐ to 16‐membered lactones. This protocol was applied to the total synthesis of (R)‐phoracantholide I.