Highly efficient and stereoselective N-vinylation of oxiranecarboxamides and unprecedented 8-endo-epoxy-arene cyclization: expedient and biomimetic synthesis of some Clausena alkaloids.
Highly efficient and stereoselective N-vinylation of oxiranecarboxamides and unprecedented 8-endo-epoxy-arene cyclization: expedient and biomimetic synthesis of some Clausena alkaloids.
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DOI：
10.1021/ol070292
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发表时间：
2007-03
期刊：
影响因子：
5.2
通讯作者：
Luo Yang;G. Deng;De‐Xian Wang;Zhi-tang Huang;Jieke Zhu;Mei-Xiang Wang
中科院分区：
文献类型：
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作者：
Luo Yang;G. Deng;De‐Xian Wang;Zhi-tang Huang;Jieke Zhu;Mei-Xiang Wang
[结构：见正文]。在 CuI/N,N-二甲基甘氨酸的催化下，环氧乙烷甲酰胺与 (Z)-1-芳基-2-溴乙烯发生高效、立体选择性的 N-乙烯基化反应，得到相应的烯酰胺。该方法已应用于天然产物对映体 (-)-(2R,3S)-SB204900 的直接合成。遵循假设的仿生途径，通过 (Z)-N-(苯基乙烯基)环氧乙酰胺的前所未有的分子内 8-内-环氧-芳烃环化，首次有效合成了 (+)-(5R,6S)-xi-Clausenamide 和 (-)-(5R,6S)-balasubramide。
[structure: see text]. Catalyzed by CuI/N,N-dimethylglycine, oxiranecarboxamides underwent a highly efficient and stereoselective N-vinylation reaction with (Z)-1-aryl-2-bromoethenes to afford the corresponding enamides. The method has been applied to a straightforward synthesis of (-)-(2R,3S)-SB204900, the enantiomer of the natural product. Following a hypothetic biomimetic pathway, both (+)-(5R,6S)-xi-Clausenamide and (-)-(5R,6S)-balasubramide have been efficiently synthesized for the first time through the unprecedented intramolecular 8-endo-epoxy-arene cyclization of (Z)-N-(phenylvinyl)oxiranecarboxamides.