Yamamoto Yuki, Tanaka Ryo, Kodama Shintaro, Nomoto Akihiro, Ogawa Akiya
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Osaka 599-8531, Japan.
Molecules. 2022 Feb 14;27(4):1284. doi: 10.3390/molecules27041284.
The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination of alkynes using the phosphorus interelement compound, tetraphenyldiphosphine monosulfide (), to stereoselectively obtain the corresponding ()--1,2-bisphosphinoalkenes, which are important transition-metal ligands. The bisphosphination reaction was performed by mixing and various alkynes and then exposing the mixture to light irradiation. Optimization of the conditions for the bisphosphination reaction resulted in a wide substrate range and excellent -selectivity. Moreover, the completely regioselective introduction of pentavalent and trivalent phosphorus groups to the terminal and internal positions of the alkynes, respectively, was achieved. We also found that the novel double-bond isomerization reaction of the synthesized bisphosphinated products occurred with a catalytic amount of a base under mild conditions. Our method for the photoinduced bisphosphination of carbon-carbon unsaturated compounds may have strong implications for both organic synthesis and organometallic and catalyst chemistry.
在光照条件下，将含有杂原子-杂原子单键的元素间化合物加成到碳-碳不饱和键上，被认为是一种原子经济性高效的方法，可用于制备含有碳-杂原子键的材料。在本研究中，我们使用元素间磷化合物四苯基二膦单硫化物（）实现了炔烃的光诱导双膦化反应，立体选择性地得到了相应的（）-1,2-双膦基烯烃，它们是重要的过渡金属配体。双膦化反应是通过将与各种炔烃混合，然后将混合物暴露于光照下进行的。双膦化反应条件的优化使得底物范围广泛且具有优异的 -选择性。此外，还实现了分别将五价和三价磷基团完全区域选择性地引入到炔烃的末端和内部位置。我们还发现，在温和条件下，合成的双膦化产物会发生新型的双键异构化反应，只需催化量的碱即可。我们用于碳-碳不饱和化合物光诱导双膦化的方法可能对有机合成以及有机金属和催化化学都具有重要意义。
