Pavel A. Volkov

Reaction of divinyl selenide with secondary phosphine chalcogenides

Divinyl telluride reacted with 2 equiv of diphenylphosphine sulfide in the presence of AIBN as radical initiator (63–68°C) to give the corresponding anti-Markovnikov adduct in 68% yield with high regioselectivity. Treatment of the addition product with aqueous hydrogen peroxide at room temperature afforded 71% of vinyldiphenylphosphine oxide. Radical addition of diphenylphosphine selenide to divinyl telluride (AIBN, 63–68°C) led to the formation of 1,1,3,3-tetraphenyldiphosphoxane 1,3-diselenide in 82% yield.

Directed synthesis of tertiary phosphine chalcogenides with pyridine and hydroxy functions

Secondary phosphine chalcogenides react with pyridine-2-, pyridine-3-, and pyridine-4-carbaldehydes under mild noncatalytic conditions (22–43°C, 1–8.5 h) to form in 81–98% yield functional tertiary phosphine chalcogenides containing pyridine and hydroxy functions.

Reaction of secondary phosphine chalcogenides with 2,2,2-trichloroacetaldehyde

The nucleophilic addition of secondary phosphine chalcogenides to 2,2,2-trichloroacetaldehyde proceeds under mild noncatalytic conditions (12–25dgC, 15–90 min) with the formation of functional tertiary phosphine chalcogenides, containing hydroxy groups in up to 98% yield. Using the method of concurrent reactions the reactivity of secondary phosphine chalcogenides in this reaction was shown to decrease in the order: (PhCH2CH2)2P(O)H ≫ (PhCH2CH2)2P(S)H > (PhCH2CH2)2P(Se)H, and the secondary bis[2-(2-pyridyl) ethyl]-phosphine oxide was more reactive than bis(2-phenethyl)phosphine oxide.

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%.

Synthesis of chalcophosphinic acid amides with pyridine rings

Bis[2-(2-pyridyl)ethyl]phosphine chalcogenides react with secondary amines in the system Et3N–CCl4, forming previously unknown bis[2-(2-pyridyl)ethyl]chalcophosphinic acid amides.

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.

A simple route to dithiophosphinic esters and diesters from secondary phosphine sulfides and thiols or dithiols

Secondary phosphine sulfides react easily at room temperature with aliphatic, aromatic and heteroaromatic thiols or dithiols in the oxidative medium Et3N/CCl4 to afford dithiophosphinic esters or diesters in 65–99% isolated yields. GRAPHICAL ABSTRACT

Atom-sparing synthesis of tertiary diphosphine dichalcogenides from acetylenes and secondary phosphine chalcogenides

Secondary phosphine oxides and phosphine sulfides react with acetylene, methylacetylene, and phenylacetylene in the presence of strong bases (KOH-DMSO, KOH-THF) by the mechanism of double nucleophilic α,β-addition to form tertiary diphosphine dioxides and diphosphine disulfides in high yield (up to 97%).