Ito Tatsuyoshi, Iwasawa Nobuharu, Takaya Jun
Department of Chemistry, School of Science, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8551, Japan.
JST, PRESTO, Honcho, Kawaguchi, Saitama, 332-0012, Japan.
Angew Chem Int Ed Engl. 2020 Jul 13;59(29):11913-11917. doi: 10.1002/anie.202004444. Epub 2020 May 18.
An unprecedented photo-promoted skeletal rearrangement reaction of phosphine-borane frustrated Lewis pairs, o-(borylaryl)phosphines, involving cleavage of an unstrained sp C-sp C σ-bond is reported. The reaction realizes an efficient synthesis of cyclic phosphonium borate compounds. The reaction mechanism via a boranorcaradiene intermediate is proposed based on theoretical calculations. This work sheds light on the new photoreactivity of phosphine-borane FLPs.
报道了一种前所未有的膦-硼烷受阻路易斯对（邻（硼芳基）膦）的光促进骨架重排反应，该反应涉及未受张力的sp C-sp C σ键的断裂。该反应实现了环状鏻硼酸酯化合物的高效合成。基于理论计算提出了通过硼杂环庚三烯中间体的反应机理。这项工作揭示了膦-硼烷受阻路易斯对的新光反应活性。
