Secondary Phosphine Sulfides Research Articles

Unexpectedly easy non-catalytic transfer of allyl group from allyl sulfides to secondary phosphine sulfides

The unexpected allylation of secondary phosphine sulfides with allyl sulfides has been found. The reaction proceeds under mild conditions (no catalyst and solvent, 80°C) to give allyldiorganylphosphine sulfides (yield up to 79%). The latter, under the reaction conditions, are able to add the initial secondary phosphine sulfides across the allyl group in the anti-Markovnikov mode to deliver propane-1,3-diylbis(diorganylphosphine sulfides), promising extractants of heavy metals and ligands for the synthesis of metal complex catalysts.

Unexpectedly Easy Noncatalytic Allyl Group Transfer from Allyl Sulfides to Secondary Phosphine Sulfides

Unexpectedly Easy Noncatalytic Allyl Group Transfer from Allyl Sulfides to Secondary Phosphine Sulfides

Synthesis of Chiral α-Substituted β-Aminophosphine Derivatives through Asymmetric Hydrophosphinylation Utilizing Secondary Phosphine Sulfides.

The organocatalytic enantioselective hydrophosphinylation of various secondary phosphine sulfides with aromatic and aliphatic nitroalkenes is presented in this study. The reaction produced chiral β-nitrophosphine sulfides with excellent yields and enantioselectivities (up to 99% yield and 99% ee). Furthermore, the chiral β-nitrophosphine sulfides can be easily converted into α-substituted β-aminophosphine, which is a family of useful P, N-ligands and phosphine catalysts.

Carbonyl Compounds: Reactants, Catalysts and Products

Ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides have been synthesized by the exhaustive regioselective addition of secondary phosphines, phosphine sulfides and phosphine selenides to available tris(4-vinylbenzyl)phosphine oxide under free-radical conditions (UV irradiation or AIBN) in good to excellent yields.

Quantum Chemical Study of the Addition of Secondary Phosphine Chalcogenides to Vinyl Selenides

DFT quantum chemical calculations at the B3PW91/6-31G(d) level of theory have shown that the addition of secondary phosphine sulfides and phosphine selenides with alkyl, phenyl, and phenylalkyl substituents to pentyl vinyl and hexyl vinyl selenides follows a molecular mechanism against the Markovnikov rule through energetically favorable eight-membered transition state, leading to the formation of tertiary phosphine chalcogenides. Secondary phosphine selenides are more reactive than the corresponding phosphine sulfides.

Oxidative Cross-Coupling of Cysteamine with Secondary Phosphine Chalcogenides: Aspects of Reaction Chemoselectivity

Cysteamine (2-aminoethanethiol) undergoes oxidative cross-coupling with secondary phosphine sulfides and phosphine selenides under mild conditions (room temperature, 2–5 h, CCl4/Et3N) to give products of monocoupling at the amino group (ethylchalcogenophosphinic amides with free SH functions) and dicoupling (l-chalcogenophosphorylamino-2-chalcogenothioethanes) in 72–85% total yield. Under similar conditions, stirring an equimolar mixture of bis(2-phenylethyl)phosphine sulfide (or selenide), 1-butylamine, and 1-butanethiol leads to the chemoselective formation of the corresponding chalcogenophosphinic amides in high yield.

Catalyst- and Solvent-Free Addition of the P–H Species to Alkenes and Alkynes: A Green Methodology for C–P Bond Formation

Traditional methods for C–P bond formation via direct addition of P–H species to unsaturated compounds are usually implemented in the presence of base and metal catalysts or radical initiators in various organic solvents. During the last five years, a novel efficient and general catalyst/initiator- and solvent-free version of the hydrophosphination and hydrophosphinylation of multiple C–C bonds with H-phosphines and their chalcogenides has begun to develop and it is attracting growing attention. This approach corresponds to the recently emerged pot-, atom-, and step-economy (PASE) green paradigm. This review covers the literature on the synthesis of useful and in-demand organophosphorus compounds via catalyst- and solvent-free addition of P–H species to alkenes and alkynes.1 Introduction2 Addition of Secondary Phosphines to Alkenes3 Hydrophosphinylation of Alkenes with Secondary Phosphine Chalcogenides3.1 Oxidative Addition of Phosphine Oxides to Vinyl Sulfides3.2 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Alkenes3.3 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Divinyl Chalcogenides3.4 Hydrophosphinylation of Alkenes with Secondary Phosphine/Chalcogen Pair (Three-Component Reactions)4 Addition of Secondary Phosphines to Alkynes5 Addition of Secondary Phosphine Chalcogenides to Alkynes6 Conclusion

Large‐Scale Programmable Synthesis of PbS Quantum Dots

The most common method of synthesizing colloidal quantum dots (QDs) relies on an increasing particle size through increasing reaction time. We demonstrate a synthesis where the QD size is programmable through the use of a secondary phosphine sulfide precursor. The reaction runs to thermodynamic completion, resulting in a desired PbS diameter for a given set of specific reaction conditions, with no need for reaction quenching or post-synthesis size-separation. Moreover, this method is shown to produce high-quality PbS QDs on the grams scale.

Green synthesis of tertiary alkylselanylphosphine chalcogenides via catalyst- and solvent-free addition of secondary phosphine chalcogenides to vinyl selenides

Secondary phosphine sulfides and phosphine selenides react with vinyl selenides under mild conditions (80–82°C, without catalyst and solvent) to form regioselectively functionalized anti-Markovnikov adducts in high yield.

ChemInform Abstract: Catalyst‐ and Solvent‐Free Stereoselective Addition of Secondary Phosphine Chalcogenides to Alkynes.

AbstractThe regio‐ and stereoselective addition of secondary phosphine sulfides and selenides to alkynes proceeds smoothly to afford anti‐Markovnikov monoadducts of (Z)‐structure in good to high 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).

ChemInform Abstract: Facile Non‐Catalyzed Synthesis of Tertiary Phosphine Sulfides by Regioselective Addition of Secondary Phosphine Sulfides to Alkenes.

AbstractThe facile protocol allows the catalyst‐ and solvent‐free addition of phosphine sulfides to terminal and internal alkenes.

Catalyst- and Solvent-Free Stereoselective Addition of Secondary Phosphine Chalcogenides to Alkynes

The addition of secondary phosphine sulfides and sele- nides to alkynes proceeds readily (80 °C, 5-13 h) without catalysts or solvents to afford regio- and stereoselectively anti-Markovnikov adducts as tertiary alkenylphosphine chalcogenides of Z-configura- tion, in 60-94% yield.

Facile Non‐Catalyzed Synthesis of Tertiary Phosphine Sulfides by Regioselective Addition of Secondary Phosphine Sulfides to Alkenes

AbstractAn atom‐economic green synthesis of tertiary phsophine sulfides has been developed based on catalyst‐ and solvent‐free addition of secondary phosphine sulfides to diverse terminal and internal alkenes (hept‐1‐ene, cyclohexene, styrenes, allyl alcohol, vinyl ethers, vinyl sulfides, vinyltrimethylsilane, 1‐vinylimidazoles, vinyl acetate). The reaction proceeds under mild conditions (80 °C, without solvent, 4–45 h) to afford chemo‐ and regioselectively the corresponding anti‐Markovnikov adducts in excellent to quantitative yields (50–99 %).

ChemInform Abstract: Three‐Component Reaction Between Secondary Phosphine Sulfides, Elemental Selenium and Vinyl Ethers: The First Examples of Markovnikov Addition of Thioselenophosphinic Acids to Double Bond.

Abstract Thioselenophosphinic acids, R2P(Se)SH, generated in situ from secondary phosphine sulfides and elemental selenium, easily add to various vinyl ethers (equimolar ratio, 100 °C, 1,4-dioxane, up to 40 min) to give earlier unknown S- and Se-[1-(organyloxy)ethyl]thioselenophosphinates, i.e., R2P(Se)SCH(Me)OR′ and R2P(S)SeCH(Me)OR′ (R, R′=alkyl, aralkyl, hetaralkyl and aryl), the S-esters being predominant (73–95% total 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.

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.

Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with secondary phosphine sulfides: Synthesis of adducts

Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with diphenylphosphine sulfide have been carried out. Reaction proceeds under radical initiation (AIBN, 63–68 °С, 2.5 h, THF, reactants molar ratio = 1:1) to afford the anti-Markovnikov monoadduct 1 and diadduct 2 in 67 and 23% yield, respectively. The former easily decomposes to give vinyldiphenylphosphine sulfide 3 (in 63% yield), ethylene and elemental tellurium, the structure of which represents mainly nano-sized powder consisting of agglomerates with average size of 350–450 nm. The comparative analysis of electron ionization mass spectra of compounds 1, 2 and 3 indicates that the presence of tellurium atom in adducts 1 and 2 reduces stability of their molecular ions and hinders the elimination of sulfur atom. Under conditions of chemical ionization of phosphine sulfides 1 and 3, the process of their protonation with CH5+ followed by the elimination of sulfur atom from [НМ]+ ion is dominant. These data are also confirmed by the results of quantum chemical calculations of the most stable protonated structures of phosphine sulfides 1 and 3.

Three-component reaction between secondary phosphine sulfides, elemental selenium and vinyl ethers: the first examples of Markovnikov addition of thioselenophosphinic acids to double bond

Thioselenophosphinic acids, R2P(Se)SH, generated in situ from secondary phosphine sulfides and elemental selenium, easily add to various vinyl ethers (equimolar ratio, 100 °C, 1,4-dioxane, up to 40 min) to give earlier unknown S- and Se-[1-(organyloxy)ethyl]thioselenophosphinates, i.e., R2P(Se)SCH(Me)OR′ and R2P(S)SeCH(Me)OR′ (R, R′=alkyl, aralkyl, hetaralkyl and aryl), the S-esters being predominant (73–95% total yield).

Chemoselective synthesis of first representatives of bis(diorganothiophosphinyl)selenides, (R2P=S)2Se, from secondary phosphine sulfides and elemental selenium

First bis(diorganothiophosphinyl)selenides, (R 2 P = S) 2 Se, have been synthesized in 74–86% yield by the chemoselective interaction of secondary phosphine sulfides with elemental selenium (1:1 molar ratio, 100 °C, 3 h, 1,4-dioxane); the alternative bis(diorganoselenophosphinyl)sulfides, (R 2 P = Se) 2 S, are not formed under these conditions. First bis(diorganothiophosphinyl)selenides, (R 2 P = S) 2 Se, have been synthesized in 74–86% yield by the chemoselective interaction of secondary phosphine sulfides with elemental selenium (1:1 molar ratio, 100 °C, 3 h, 1,4-dioxane); the alternative bis(diorganoselenophosphinyl)sulfides, (R 2 P = Se) 2 S, are not formed under these conditions. ► First representatives of bis(diorganothiophosphinyl)selenides were prepared. ► Reaction between secondary phosphine sulfides and selenium was investigated. ► The X-ray structures of (Cy 2 P=S) 2 Se and (Cy 2 P=S) 2 Se 2 were determined.