[3,3]-Sigmatropic rearrangements of propargyl alkynyl ethers. Synthesis of complex dienoates and unsaturated lactones
[3,3]-Sigmatropic rearrangements of propargyl alkynyl ethers. Synthesis of complex dienoates and unsaturated lactones
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DOI：
10.1039/d2ob02121h
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发表时间：
2023-01-06
影响因子：
3.2
通讯作者：
Minehan，Thomas G.
中科院分区：
文献类型：
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作者：
Sosa，Juan R.;Tudjarian，Armen A.;Minehan，Thomas G.
在我们对1-炔基醚的低温重排研究的扩展中，我们在本文中描述了原位形成的炔丙基炔基醚的[3，3]-σ迁移重排为丙二烯基烯酮，其在叔丁醇加成时以良好的产率提供复杂的叔丁基-（2 E，4 Z）-二烯酸酯2。类似地，原位形成的炔丙基锂代炔基醚的σ迁移重排在甲醇加成时产生甲基-（2 Z，4 Z）-二烯酸酯4，或在醛或酮加成到炔酸丙二烯酯中间体时产生不饱和内酯6。
In an extension of our studies on low-temperature rearrangements of 1-alkynyl ethers, we describe herein the [3,3]-sigmatropic rearrangement of in situ formed propargyl alkynyl ethers to allenyl ketenes, which furnish complex tert-butyl-(2E,4Z)-dienoates 2 in good yields upon tert-butanol addition. Similarly, sigmatropic rearrangements of in situ formed propargyl lithioalkynyl ethers yield methyl-(2Z,4Z)-dienoates 4 upon methanol addition or unsaturated lactones 6 upon aldehyde or ketone addition to the allenyl ynolate intermediate.