Department of Applied Chemistry, Graduate School of Engineering , Osaka University , Suita, Osaka 565-0871 , Japan.
Department of Chemical Science and Engineering, School of Materials and Chemical Technology , Tokyo Institute of Technology , 2-12-1 O-okayama , Meguro-ku , Tokyo 152-8552 , Japan.
Org Lett. 2018 Jun 15;20(12):3670-3673. doi: 10.1021/acs.orglett.8b01470. Epub 2018 Jun 6.
A diphosphination of arynes with diphosphines has been developed. The reaction of stable aryne precursors, 2-(trimethylsilyl)aryl triflates, with tetraaryldiphosphines proceeds in the presence of fluorine- or carbonate-based activators to deliver the corresponding diphosphinated products, sterically and electronically tuned 1,2-bis(diphenylphosphino)benzene (dppbz) derivatives, which can find wide application in transition metal catalysis and material science. Additionally, preliminary computational studies on the reaction mechanism are also reported.
芳基炔与二膦的双膦化反应已经发展起来。在氟化物或碳酸盐基活化剂的存在下,稳定的芳基炔前体,2-(三甲基甲硅烷基)芳基三氟甲磺酸酯与四芳基二膦反应,生成相应的双膦化产物,即空间和电子可调的 1,2-双(二苯基膦基)苯(dppbz)衍生物,这些产物在过渡金属催化和材料科学中有广泛的应用。此外,还报道了该反应机理的初步计算研究。