Normandie Université, LCMT, ENSICAEN, UNICAEN, CNRS , 6, Boulevard Maréchal Juin, Caen 14000 France.
Institut de Science des Matériaux de Mulhouse IS2M - UMR CNRS 7361 - UHA , 15, rue Jean Starcky, Mulhouse 68057 Cedex, France.
Org Lett. 2016 Nov 18;18(22):5900-5903. doi: 10.1021/acs.orglett.6b02983. Epub 2016 Nov 4.
A novel and efficient method for the generation of phosphinoyl radicals from the combination of diphenyliodonium salt (PhI,OTf) with triethylamine (EtN) in the presence of secondary phosphine oxides is reported. By employing this practical and simple approach, a large variety of 6-phosphorylated phenanthridines have been synthesized through the addition of phosphinoyl radicals to isonitriles as radical acceptors. The reaction works smoothly in the absence of any transition metal or photocatalyst. On the basis of electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, the mechanism of this reaction is discussed.
报道了一种新颖、高效的方法，即在二苯基碘𬭩盐（PhI，OTf）与三乙胺（EtN）的组合存在下，通过二级氧化膦生成膦酰基自由基。通过采用这种实用且简单的方法，通过将膦酰基自由基加成到异腈作为自由基受体，合成了多种 6-磷酸化菲啶。该反应在没有任何过渡金属或光催化剂的情况下顺利进行。基于电子顺磁共振（EPR）和密度泛函理论（DFT）计算，讨论了该反应的机理。
