通过炔键互变异构原位形成丙二烯促进带有末端炔或腈的[4+2]环加成反应。
In Situ Allene Formation via Alkyne Tautomerization to Promote [4 + 2]-Cycloadditions with a Pendant Alkyne or Nitrile.
机构信息
Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
出版信息
Org Lett. 2022 Apr 1;24(12):2327-2331. doi: 10.1021/acs.orglett.2c00491. Epub 2022 Mar 21.
Abstract
We have explored the net-[4 + 2]-cycloadditions of a variety of aryl (or alkenyl) alkynes. Tautomerization via base-catalyzed alkyne-to-allene isomerization produces a transient allene, which undergoes stepwise cyclization with not only a pendant alkyne but also a nitrile. The operative mechanisms for these reactions were studied by density functional theory and compared with the slower thermal cyclization of the precursor alkyne.
摘要
我们已经探索了各种芳基（或烯基）炔烃的净-[4 + 2]-环加成反应。通过碱催化的炔烃到丙二烯异构化的互变异构化产生瞬态丙二烯，它不仅与悬垂炔烃而且与腈逐步环化。这些反应的操作机制通过密度泛函理论进行了研究，并与前体炔烃较慢的热环化进行了比较。
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