Kseniya O. Khrapova

Chlorination of secondary phosphine chalcogenides with carbon tetrachloride in the absence of bases

The interaction of bis(2-phenylethyl)phosphine sulfide, bis(2-phenylethyl)phosphine selenide and bis[2-(2-phenyl)propyl]phosphine selenide with carbon tetrachloride under heating (80°C, 8–20 h) leads to the formation of the corresponding chlorophosphine chalcogenides with the yield of 80–90%.

Three-Component Reaction of 4-Methylpyridine with Alkyl Propiolates and Secondary Phosphine Chalcogenides

The reaction between 4-methylpyridine, alkyl propiolates, and secondary phosphine oxides proceeded as N-vinylation-C-phosphorylation with stereo- and regioselective formation of (E)-N-ethenyl-C2- phosphoryl-1,2-dihydropyridines [when using bis(2-phenylethyl)phosphine oxide] or (E)-N-ethenyl-C4- phosphoryl-1,4-dihydropyridines (when using diphenylphosphine oxide). The process occurred at 60–62°C within 3 h to give functional dihydropyridines in 40–82% yield. Under similar conditions, bis(2-phenylethyl) phosphine sulfide and selenide reacted with alkyl propiolates preferably by nucleophilic PH-monoaddition at the triple bond.

Metal-free site selective cross-coupling of pyridines with secondary phosphine chalcogenides using acylacetylenes as oxidants

Pyridines undergo site selective cross-coupling with secondary phosphine chalcogenides (oxides, sulfides, and selenides) in the presence of acylphenylacetylenes under metal-free mild conditions (70-75 °C, MeCN) to afford 4-chalcogenophosphoryl pyridines in up to 71% yield. In this new type of SNHAr reaction acylacetylenes act as oxidants, being stereoselectively reduced to the corresponding olefins of the E-configuration.

Unexpected Carbon–Selenium Bond Formation in the Reaction of Secondary Phosphine Selenides with Benzoylphenylacetylene

Secondary phosphine selenides reacted as selenating agents with benzoylphenylacetylene in wet acetonitrile (70–72°C) to give bis(2-benzoyl-1-phenylvinyl) selenide in up to 43% yield.