Five Membered Heterocyclic Nitrenium Ions: Generation, Structure, Reactivity

在有机动力学项目的支持下，鲁道夫·A·阿布拉莫维奇博士将研究五元杂环镍离子的合成和化学。这些物种是高活性的中间体，其化学反应活性是物理有机化学家和理论化学家感兴趣的。除了它们固有的理论兴趣外，这些物种作为一类新的亲电的伯胺化试剂具有潜在的重要意义，也是合成有机化学家感兴趣的。特别令人感兴趣的是这些物种与其他阳离子体系发生异构化的潜在能力。我们将用离子回旋共振质谱仪研究亲核剂对这些杂环异构化离子的产生和捕获，以获得有关硝离子中pi-to-sigma“电子异构化”操作的信息。捕获实验也将在溶液中进行，考虑到相同的目标。对由此得到的各种反应产物的详细分析可望深入了解每种情况下存在的活性中间体(S)的性质。

With support from the Organic Dynamics Program, Dr. Rudolph A. Abramovitch will study the synthesis and chemistry of five-membered heterocyclic nitrenium ions. These species are highly reactive intermediates whose chemical reactivity is of interest to physical organic chemists and to theoretical chemists. In addition to their inherent theoretical interest, these species are of potential importance as a new class of electrophilic primary aminating agents that are of interest to synthetic organic chemists as well. Of particular interest is the potential ability of these species to undergo isomerization to other cationic systems. The generation and trapping of these heterocyclic sigma-cations by nucleophiles will be studied via ion cyclotron resonance mass spectrometry in an effort to obtain information concerning the operation of pi-to-sigma "electronic isomerizations" in the nitrenium ions. Trapping experiments will also be performed in solution with the same objective in mind. Detailed analysis of the various reaction products thereby obtained is expected to afford insight into the nature of the reactive intermediate(s) present in each case.