苯炔与β-二酮硫醚参与的氧杂-[2,3]-σ重排反应研究

Study on oxa-[2,3]sigmatropic rearrangement involving arynes andβ-diketo thioethers

重排反应是有机化学中的基本反应,高效有用的重排反应往往可以巧妙快速的合成重要的化合物。苯炔与β-二酮硫醚的反应中,经过硫叶立德中间体和并不常见的羰基极性反转过程,得到一种新的、有趣的氧杂-[2,3]-σ重排反应现象,利用该反应可以构建多种高度官能团化的烯醇硫醚衍生物。

Rearrangement reactions are fundamental transformations in organic chemistry that involve the migration of the skeletal carbon architecture and/or the most remarkable bond reorganization and thus allow the rapid assembly of important structural frameworks.Herein,an oxa-[2,3]sigmatropic rearrangement is reported featuring the umpolung of ketones,and the in situ-generated sulfur ylides fromβ-diketo thioethers and arynes undergo efficient rearrangement allowing the facile and robust synthesis of functionalized enol thioethers in high yields and excellent functional group compatibility.