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 Feb 11;25(9):2295-2302. doi: 10.1002/chem.201805114. Epub 2019 Jan 21.
Bis-phosphanated compounds are regarded as the most ubiquitous privileged ligand structures in transition-metal catalysis. The development of highly atom economical reactions is of great importance for their syntheses because less atom economical methods often require complicated purification procedures under inert atmospheres to remove excess starting materials and byproducts. Herein, the photoinduced addition reactions of diphosphane monosulfides bearing P (S)-P single bonds to alkenes is disclosed. These reactions require only equimolar amounts of the diphosphane monosulfide relative to the alkene and facilitate highly selective introduction of two different types of phosphorus-containing groups, such as thiophosphoryl and phosphanyl groups, into a variety of alkenes without any catalyst, base, or additive.
双膦化合物被认为是过渡金属催化中最普遍的特权配体结构。由于较少原子经济性的方法通常需要在惰性气氛下进行复杂的纯化程序来去除过量的起始原料和副产物，因此开发高原子经济性的反应对于它们的合成非常重要。在此，公开了含有 P(S)-P 单键的二膦单硫化物与烯烃的光诱导加成反应。这些反应仅需要与烯烃等摩尔量的二膦单硫化物，并促进在各种烯烃中高度选择性地引入两种不同类型的含磷基团，如硫代膦酰基和膦基，而无需任何催化剂、碱或添加剂。
