Richardson Robert D, Desaize Magalie, Wirth Thomas
School of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, UK.
Chemistry. 2007;13(23):6745-54. doi: 10.1002/chem.200700306.
By detailed study of the possible side reactions in the previously reported aziridination of alkenes with N-aminoheterocycles mediated by hypervalent iodine reagents, the requirements to make this reaction catalytic in iodoarene have been determined. The reaction requires an oxidant that will oxidise iodoarenes but that does not oxidise alkenes, but it is possible that no such oxidant actually exists! A method in which the hypervalent iodine reagent can be recycled without the need for reisolation is possible. Further study into the mechanism of this reaction gives tentative evidence that the reaction proceeds through formation of an aminoiodane that reacts directly with the alkene, contrary to previous literature reports in which an acetoxyamine intermediate is suggested. The temperature effect of this reaction is remarkable.
通过对先前报道的用高价碘试剂介导的烯烃与N-氨基杂环进行氮杂环丙烷化反应中可能的副反应进行详细研究，确定了使该反应在碘芳烃中具有催化作用的条件。该反应需要一种能氧化碘芳烃但不氧化烯烃的氧化剂，但实际上可能不存在这样的氧化剂！有可能实现一种无需重新分离就能循环使用高价碘试剂的方法。对该反应机理的进一步研究提供了初步证据，表明该反应是通过形成直接与烯烃反应的氨基碘烷进行的，这与先前文献报道中提出的乙酰氧基胺中间体的情况相反。该反应的温度效应显著。
