叠氮化物作用下受阻路易斯对化学的新认识。
New Insights in Frustrated Lewis Pair Chemistry with Azides.
机构信息
Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1090 GD, Amsterdam, The Netherlands.
Department of Chemistry, University of Helsinki, A. I. Virtasen aukio 1, PO Box 55, 00014, Helsinki, Finland.
出版信息
Chemistry. 2019 Oct 17;25(58):13299-13308. doi: 10.1002/chem.201902710. Epub 2019 Sep 9.
The geminal frustrated Lewis pair (FLP) tBu PCH BPh (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes-N and tBu-N are used. The reaction of 1 with Me Si-N is believed to follow the same course, yet subsequent N elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.
偕二茂铁受阻路易斯对（FLP）tBu PCH BPh（1）与苯基叠氮化物、均三甲苯叠氮化物和叔丁基叠氮化物反应，分别得到可分离的六元、五元、四元环产物。DFT 计算表明，所有产物的形成均通过六元环结构进行，该结构在带有一个 N-苯基基团时热力学稳定，但当使用空间位阻更大的 Mes-N 和 tBu-N 时会发生重排。与 Me Si-N 的反应被认为遵循相同的途径，但随后会发生 N 消除，生成四元杂环（5），可视为一种形式的 FLP-三甲基硅基氮烯加合物。化合物 5 与盐酸或四氟硼酸反应，对苯基异氰酸酯表现出受阻路易斯对反应活性。
Zotero 插件