O. V. Vysotskaya

Non-catalytic addition of 1,2,4-triazole to nucleophilic and electrophilic alkenes

Non-catalytic addition of 1,2,4-triazole to vinyl ethers and esters occurs on heating (65-175°C, 4-20 h) to give Markovnikov adducts (yield 30-100%). Electron-deficient alkenes (acrylonitrile, acrylic acid, 4-phenyl-3-buten-2-one) react with 1,2,4-triazole (78-190°C, 4-20 h) to give anti-Markovnikov adducts in yields of 45-83%.

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XVI*. Vinylation of Alcohols of the Furan Series under Atmospheric Pressure

Abstract2-Hydroxymethylfuran and 2-hydroxymethyltetrahydrofuran reacted with acetylene in the superbasic catalytic system KOH-DMSO at 75-85°C under atmospheric pressure to give in 1.5–3 h the corresponding 2-vinyloxymethyl derivatives in 88 and 91% yield, respectively.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XV. Vinylation of 2-hydroxymethylfuran

Abstract2-Hydroxymethylfuran reacted with acetylene in superbasic catalytic systems MOH-DMSO (M = Na, K) under mild temperature conditions (75–85°C, 1–2 h), yielding 80% of 2-vinyloxymethylfuran. The product, as well as acetaldehyde acetals derived therefrom, turned out to be promising as modifiers for electrolyte in lithium-sulfur rechargeable batteries.

Functional Acetal Methacrylates: III. * Electrophilic Addition of Diols to 2-(Vinyloxy)ethyl Methacrylate

Reactions of 2-(vinyloxy)ethyl methacrylate with diols [ethylene glycol, diethylene glycol, triethylene glycol, oligoethylene glycol-400, Z-2-butene-1,4-diol, 2-butyne-1,4-diol, 1,1,3,3-tetramethyl-1,3-bis(3-hydroxypropyl)disiloxane, 2,2-bis(4-hydroxyphenyl)propane] and polyols (glycerol, pentaerythritol) under electrophilic conditions (1 wt% of CF3COOH, 20-60°C, 1-3 h) result in quantitative formation of functional acetal methacrylates.

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.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVII. Vinyl ethers with furyl and cycloacetal fragments: Synthesis and structure

Abstract4-Hydroxymethyl-2-(2-furyl)-1,3-dioxolane and 5-hydroxy-2-(2-furyl)-1,3-dioxane consisting of mixtures of cis- and trans-isomers react with acetylene in the superbasic catalytic system KOHH-DMSO at the atmospheric or higher pressure (80–85°C, 2–3 h) giving the corresponding vinyl ethers in 88–90% yield. The ratio of the structural and configurational isomers in vinyl ethers remains the same as in the initial compounds.

Vinylation of hydroxy-containing cyclic formaldehyde acetals with acetylene

Nucleophilic addition of alcohols having cyclic acetal fragments to acetylene smoothly occurs under relatively mild conditions (KOH, 100–125°C, 1–2 h, initial acetylene pressure 11–12 atm) to give the corresponding vinyl ethers in 80–83% yield.

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

Electrophilic and Nucleophilic Addition of Alkanethiols to 2-Vinyloxyethylmethacrylate

Under acid- or base-catalyzed conditions, thiols add regio- and chemos-electively either to vinyloxy or methacrylate group of vinyloxyalkyl-methacrylates to give polyfunctional methacrylates or polyfunctional vinyl ethers, respectively.

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