4.5 Article

Reactivity of a Cationic Bismuth Amide towards Unsymmetric Heterocumulenes

期刊

CHEMPLUSCHEM
卷 88, 期 7, 页码 -

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cplu.202200455

关键词

bismuth; cations; hard and soft acids and bases; heterocumulenes; insertion reactions

向作者/读者索取更多资源

The reactivity of a literature-known, ring-strained bismuth amide cation towards unsymmetric heterocumulene substrates has been investigated. Reactions with ketenes, isocyanates, and isothiocyanates proceed via facile insertion of the heterocumulene in the Bi-N bond of the cationic bismuth amide. Unexpected differences in the regioselectivity of these insertion reactions have been observed, leading to unprecedented heterocycle motifs. Parameters controlling the regioselectivity have been identified through experimental and theoretical investigations.
The reactivity of a literature-known, ring-strained bismuth amide cation towards a range of unsymmetric heterocumulene substrates has been investigated. Reactions with ketenes R2C=C=O (R=Me, Ph), isocyanates R'N=C=O, and isothiocyanates R'N=C=S (R'=Ph, 4-CF3-C6H4) proceed via facile insertion of the heterocumulene in the Bi-N bond of the cationic bismuth amide. Unexpectedly pronounced differences in the regioselectivity of these insertion reactions have been observed, yielding a rich variety of heterocycle motifs (BiC2NC2, BiC2NCO, BiC2NCS, BiC2NCN), some of which are unprecedented. Parameters that control the regioselectivity of the insertion reactions have been identified and are discussed based on experimental and theoretical investigations. Analytical techniques applied in this work include heteronuclear and two-dimensional NMR spectroscopy, IR spectroscopy, elemental analysis, single-crystal X-ray diffraction analyses, and DFT calculations.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.5
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据