Nikita A. Kolyvanov

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVIII. Vinylation of phenols and naphthols with acetylene

Phenols and naphthols react with acetylene in a superbasic system KOH-DMSO forming the corresponding aryl vinyl ethers in up to 80% yields.

Electrophilic addition of thioselenophosphinic acids to vinyl sulfides and selenides

The thioselenophosphinic acids, R2P(Se)SH (R = Ph, Cy, aralkyl), prepared by acidification of the sodium salts or generated in situ by reaction of secondary phosphine sulfides with elemental selenium, add easily to diverse vinyl sulfides and vinyl selenides in a Markovnikov manner to give the corresponding S- and Se-esters in a ∼60:40 molar ratio (83–96% total yield). GRAPHICAL ABSTRACT

Atom-economic synthesis of highly branched functional ‘tripod-like’ triphosphine sulfides

The tertiary polyfunctional triphosphine sulfides with amino and (or) ether groups have been synthesized in excellent yields by the exhaustive regioselective (in anti-Markovnikov manner) addition of secondary phosphines sulfides to trivinyl ethers of aminotriols and triols under free-radical conditions (UV-irradiation, 1.5–5 h). GRAPHICAL ABSTRACT

Unexpected formation of methylsulfanylmethyl phenyl ether at vinylation of phenol with acetylene in the K2CO3-DMSO system

Meanwhile, the examples of methylsulfanylmethylation of phenols with dimethylsulfoxide are known [1, 2]. So, after prolonged boiling (up to 30 h) of phenol in anhydrous DMSO a mixture of products of Оand С-2methylsulfanylmethylation in the ratio 2.5 : 1 with total yield of 14% [1] was obtained (Scheme 2). In the presence of bases (carbonates of alkali metals, amines) and tert-butyl bromide the reaction of phenol with DMSO (35–40°С, 24 h) proceeds along Оand О,Сalkylation with predominant formation of methylsulfanylmethyl phenyl ether (products yield not reported) [2].

Synthesis of oxazolidinylphosphine chalcogenides from aminoethyl vinyl ethers

N-(2-Vinyloxyethyl)phosphinothioamides and -phosphinoselenoamides prepared by oxidative cross-coupling of 2-vinyloxyethylamine with secondary phosphine chalcogenides undergo thermal (75–100 °C) cyclization into the corresponding 3-(diorganylchalcogenophosphoryl)-2-methyl-1,3-oxazolidines in 80–90% yields.