Synthetic efforts toward the Lycopodium alkaloids inspires a hydrogen iodide mediated method for the hydroamination and hydroetherification of olefins.
Synthetic efforts toward the Lycopodium alkaloids inspires a hydrogen iodide mediated method for the hydroamination and hydroetherification of olefins.
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DOI：
10.1002/chem.201406242
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发表时间：
2015-03
期刊：
影响因子：
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通讯作者：
P. Leger;Rebecca A. Murphy;E. Pushkarskaya;Richmond Sarpong
中科院分区：
文献类型：
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作者：
P. Leger;Rebecca A. Murphy;E. Pushkarskaya;Richmond Sarpong
公开了通过“Heathcock型”6-5-9三环全合成多种福西替胺型石松生物碱的进展。该路线的特点是通过分子间狄尔斯-阿尔德环加成反应快速形成 6-5 稠合自行车，并通过高度化学选择性的定向氢化反应构建氮烷片段。在进行这些合成研究时，发现三甲基碘化硅可以进行氢胺化反应，以提供沙雷汀和相关天然产物的四环核心。这一观察结果已扩展到利用催化“无水”HI（由三甲基碘硅烷和水原位生成）对未活化烯烃与甲苯磺酰胺进行室温加氢胺化的通用方法。碘阴离子的存在对于布朗斯台德酸催化方案的成功至关重要，这可能是由于其作为弱配位阴离子的功能。这些条件还影响醇与未活化烯烃的类似加氢醚化反应。
Progress toward the total syntheses of a diverse set of fawcettimine-type Lycopodium alkaloids via a "Heathcock-type" 6-5-9 tricycle is disclosed. This route features an intermolecular Diels-Alder cycloaddition to rapidly furnish the 6-5-fused bicycle and a highly chemoselective directed hydrogenation to build the azonane fragment. While conducting these synthetic studies, trimethylsilyl iodide was found to effect a hydroamination reaction to furnish the tetracyclic core of serratine and related natural products. This observation has been expanded into a general method for the room temperature hydroamination of unactivated olefins with tosylamides utilizing catalytic "anhydrous" HI (generated in situ from trimethylsilyl iodide and water). The presence of the iodide anion is critical to the success of this Brønsted acid catalyzed protocol, possibly due to its function as a weakly coordinating anion. These conditions also effect the analogous hydroetherification reaction of alcohols with unactivated olefins.