Yamamoto Yuki, Kawaguchi Shin-Ichi, Nishimura Misaki, Sato Yuki, Shimada Yoshihisa, Tabuchi Akihiro, 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.
J Org Chem. 2020 Nov 20;85(22):14684-14696. doi: 10.1021/acs.joc.0c01926. Epub 2020 Nov 9.
This study shows that phosphorus sources can be recycled using the appropriate fluorous phosphine in the Wittig reaction. The designed fluorous phosphine, which has an ethylene spacer between its phosphorus atom and the perfluoroalkyl group, was synthesized from air-stable phosphine reagents. The synthesized phosphine can be used for the Wittig reaction process to obtain various alkenes in adequate yields and stereoselectivity. The concomitantly formed fluorous phosphine oxide was extracted from the reaction mixture using a fluorous biphasic system. The fluorous phosphine was regenerated by reducing the fluorous phosphine oxide with diisobutylaluminum hydride. Finally, a series of gram scale phosphorus recycling processes were performed, which included the Wittig reaction, separation, reduction, and reuse.
本研究表明，在维蒂希反应中使用合适的氟代膦可以实现磷源的循环利用。所设计的氟代膦在其磷原子和全氟烷基之间有一个乙烯间隔基，它由空气稳定的膦试剂合成。合成的膦可用于维蒂希反应过程，以适当的产率和立体选择性获得各种烯烃。使用氟两相体系从反应混合物中萃取同时形成的氟代氧化膦。通过用二异丁基氢化铝还原氟代氧化膦来再生氟代膦。最后，进行了一系列克级规模的磷循环过程，包括维蒂希反应、分离、还原和再利用。
