Stereoselective free-radical addition of secondary phosphine selenides to aromatic acetylenes

Free-radical addition (AIBN, 65-70 °C, 5-7 h) of secondary phosphine selenides to arylacetylenes proceeds stereoselectively to give anti-Markovnikov adducts of predominantly Z-configuration (up to 97%) in 60-80% isolated yields, thus representing a rare example of stereoselective free-radical addition to the triple bond. Microwave irradiation (600 W) of the reactants with the same content of AIBN reduces the reaction time to 8 min though compromises the stereoselectivity. Under UV-initiation the reaction loses its stereoselectivity due to isomerization of the primary Z-adducts. In this reaction, a specific facilitating and Z-configuration-controlling effect of aromatic substituents at the triple bond has been revealed.     

Polyfluoroalkyl Phosphates Bearing Propargyl Substituents

Russian Journal of General Chemistry - Polyfluoroalkyl dichlorophosphates react easily with propargyl alcohol under mild conditions (22–62°С, 3 h, pyridine-toluene) to form...     

First Examples of the Atherton–Todd‐Like Reaction in the Absence of Bases

Oxidative cross‐coupling between secondary phosphine chalcogenides and alcohols or phenols proceeds in CCl₄ medium at 80–82°C to afford phosphinoсhalcogenоic O‐esters in up to 92% yield. These couplings represent first examples of the Atherton–Todd‐like reaction occurring in the absence of bases.     

Novel quinine,lupinine, and anabasine derivatives containing dithiophosphinate groups

A three-component, atom-economic reaction between natural quinine, lupinine, or anabasine, secondary phosphines, and elemental sulfur occurs under mild conditions to yield previously unknown optically active dithiophosphinates.     

Synthesis of first representatives of alkaline-earth metal diselenophosphinates

A three-component reaction between secondary phosphines, elemental selenium, and calcium or barium hydroxides in a molar ratio of 1: 2: 0.5 proceeds under mild conditions (70?C75 °C, 10 min, aqueous ethanol) to give previously unknown Ca and Ba diselenophosphinates (78?C89%).