S. I. Verkhoturova

Radical addition of secondary phosphine chalcogenides to allylamine: Atom-economic synthesis of aminopropylphosphine chalcogenides

Secondary phosphine sulfides and phosphine selenides react with allylamine under the conditions of radical initiation (UV or AIBN) to form the anti-Markovnikov adducts in up to 93 % yield.

Redox reaction of red phosphorus with hydrosulfide anions in DMSO

Received April 3, 2008 LETTERS TO THE EDITOR ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1816–1818.

Synthesis and Isomer Composition of 2-Polyfluoroalkoxy-1,3,2-dioxaphospholanes and -phosphinanes

Polyfluoroalkanols readily reacted with 2-chloro-1,3,2-dioxaphospholanes and 2-chloro-1,3,2-dioxaphosphinanes in hexane in the presence of triethylamine (–10 to 25°C, 5 h) to give 2-polyfluoroalkoxy-1,3,2- dioxaphospholanes and 2-polyfluoroalkoxy-1,3,2-dioxaphosphinanes in 48–72% yield. The products were found to exist as mixtures of cis and trans isomers with the trans isomer predominating for the phospholanes and cis isomer predominating for the phosphinanes according to the 1H, 13C, 19F, and 31P NMR data.

Synthesis of polyfluoralkylated 1,3,2-dioxaphospholane and 1,3,2-dioxaphosphorinane oxides

Polyfluoroalkyl dichlorophosphates easily react with 1,2- or 1,3-alkanediols in a system pyridine–diethyl ether and afford 2-polyfluoroalkoxy-1,3,2-dioxaphospholane oxides or 2-polyfluoroalkoxy-1,3,2-dioxaphosphorinane oxides. In similar conditions the reaction of methyl dichlorophosphate with 1,2- and 1,3-alkanediols proceeds less effectively.

Phosphorylation of alkyl methanesulfonates with elemental phosphorus in a strongly basic medium: Synthesis of alkylphosphinic acids

Alkyl methanesulfonates were for the first time introduced in the reaction of direct phosphorylation of electrophiles with elemental phosphorus in strongly basic media to synthesize alkylphosphinic acids in yields of up to 40%.

Reaction of secondary phosphine chalcogenides with diallylamine

Diphenyl- or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl phosphine chalcogenides. The yield and the ratio of the products depend on the structure of the starting secondary phosphine chalcogenides.

Nucleophilic Addition of Phosphine to Vinyl Sulfoxides

Reaction of addition of phosphine to multiple bonds represents an obvious alternative to the synthesis of organophosphorus compounds by the use of phosphorus halogenides, opening the route to atomsparing design of various phosphines and their derivatives. In spite of its attractiveness up to now this alternative has not been systematically developed although the addition of phosphine to some alkenes and acetylenes is described in a number of publications [1, 2]. So far nothing is known about the addition of phosphine to vinyl sulfoxides. At the same time, this reaction opens a direct one-step route to difficultly accessible phosphines with sulfoxide groups, promising semilabile chelating ligands [3, 4] and intermediates for preparation of, e.g., radioactive diagnosticums [5–7].