Sato Yuki, Nishimura Misaki, Kawaguchi Shin-Ichi, Nomoto Akihiro, Ogawa Akiya
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka, 599-8531, Japan.
Center for Education and Research in Agricultural Innovation, Faculty of Agriculture, Saga University, 152-1 Shonan-cho Karatsu, Saga, 847-0021, Japan.
Chemistry. 2019 May 10;25(27):6797-6806. doi: 10.1002/chem.201900073. Epub 2019 Apr 25.
The facile synthesis of organophosphorus compounds is of great importance for the development of new synthetic methods by using air-stable sources of phosphorus. In this respect, a synthetic method that is based on a reductive rearrangement and is capable of converting air-stable pentavalent phosphorus compounds into reactive trivalent phosphorus compounds is a powerful tool. Tetraphenyldiphosphine disulfide, which is a shelf-stable solid, was the focus of this study, and it was shown to undergo reductive rearrangement to trigger the bisthiophosphinylation of a variety of alkenes, such as terminal, cyclic, internal, and branched alkenes, 1,3-dienes, and terminal alkynes when exposed to light without any catalyst, base, or additive.
利用空气稳定的磷源开发新的合成方法时,有机磷化合物的简便合成具有重要意义。在这方面,基于还原重排且能够将空气稳定的五价磷化合物转化为活性三价磷化合物的合成方法是一种强大的工具。本研究的重点是四苯基二膦二硫化物,它是一种货架稳定的固体,结果表明,在无任何催化剂、碱或添加剂的情况下,该化合物在光照下会发生还原重排,从而引发多种烯烃(如末端烯烃、环状烯烃、内烯烃和支链烯烃)、1,3 - 二烯和末端炔烃的双硫代膦酰化反应。