Addition Of Secondary Phosphine Chalcogenides Research Articles

Catalyst-free addition of secondary phosphine chalcogenides to pyrazolecarbaldehydes

(Chalcogenophosphoryl)(hydroxyl)methyl-substituted pyrazoles were obtained by catalyst-free reaction between 4- and 5-pyrazolecarbaldehydes and secondary phosphine chalcogenides R2P(X)H [R = Ph, (CH2)2Ph, X = O, S, Se] at 23–50 °C in toluene.

Structural effect in the reductive vinylation/phosphorylation of pyridines with alkyl propiolates and secondary phosphine chalcogenides: protonation vs. zwitterion generation

The non-catalyzed reaction of 2- and 3-substituted pyridines with alkyl propiolates and secondary phosphine chalcogenides (50–52 °C, MeCN) produces stereo-, regio- and chemoselectively 1-[(E)-2-(alkoxycarbonyl)ethenyl]-4-chalcogenophosphoryl- 1,4-dihydropyridines in 57–90% yields, the adducts of pyridines with alkyl propiolates being the zwitterionic intermediates. 4-Methylpyridine mainly catalyzes nucleophilic addition of secondary phosphine chalcogenides to alkyl propiolates.

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

Non-catalyzed addition of secondary phosphine chalcogenides to divinyl chalcogenides under solvent-free conditions

ABSTRACT Secondary phosphine chalcogenides, R2PX (R═(CH2)2Ph, Ph; X = S, Se), react with divinyl chalcogenides, (CH2═CH)2Y (Y = S, Se, Te), at the 2:1 molar ratio (80–82°C, 56–80 h) in the absence of both catalysts (initiators) and solvents to quantitatively afford the corresponding anti-Markovnikov diadducts. Even at the equimolar reactant ratio, the diadducts are the major products, though monoadducts are also formed. When Y = Te, vinylphosphine chalcogenides and metal Te are obtained, thus showing that divinyl telluride behaves as the vinylating agent.

ChemInform Abstract: An Expedient Access to γ‐Ketophosphine Chalcogenides via the Chemo‐ and Regioselective Addition of Secondary Phosphine Chalcogenides to β,γ‐Ethylenic Ketones.

γ-Ketophosphine chalcogenides, precursors for plethora of novel functionalized phosphine chalcogenides and phosphines, are synthesized by chemo- and regioselective addition of secondary phosphine chalcogenides to β,γ-ethylenic ketones under catalyst- and solvent-free conditions (80–100°C, 8–70 h) in excellent yields. The straightforward superbase-catalyzed synthesis of starting β,γ-ethylenic ketones from ketones and acetylenes insures the expedient access to the target γ-ketophosphine chalcogenides.

ChemInform Abstract: Catalyst‐ and Solvent‐Free Rapid Addition of Secondary Phosphine Chalcogenides to Aldehydes: Another Click Chemistry.

AbstractSignificantly shorter reaction times together with higher yields are the benefits when the addition reaction is carried out under solvent‐free conditions.

An Expedient Access to γ‐Ketophosphine Chalcogenides via the Chemo‐ and Regioselective Addition of Secondary Phosphine Chalcogenides to β,γ‐Ethylenic Ketones

ABSTRACTγ‐Ketophosphine chalcogenides, precursors for plethora of novel functionalized phosphine chalcogenides and phosphines, are synthesized by chemo‐ and regioselective addition of secondary phosphine chalcogenides to β,γ‐ethylenic ketones under catalyst‐ and solvent‐free conditions (80–100°C, 8–70 h) in excellent yields. The straightforward superbase‐catalyzed synthesis of starting β,γ‐ethylenic ketones from ketones and acetylenes insures the expedient access to the target γ‐ketophosphine chalcogenides.

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.

Catalyst- and Solvent-Free Rapid Addition of Secondary Phosphine Chalcogenides to Aldehydes: Another Click Chemistry

An efficient catalyst- and solvent-free method for the synthesis of tertiary α-hydroxyphosphine chalcogenides, via the almost quantitative addition of secondary phosphine chalcogenides to diverse aldehydes under mild conditions (20–52 °C, from 10 min to 5 h), is reported.

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.

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.

One-Pot Vinylation of Secondary Phosphine Chalcogenides with Vinyl Sulfoxides

A facile, one-pot vinylation of secondary phosphine chalcogenides with alkyl(or aryl) vinyl sulfoxides has been elaborated. The vinylation comprises the nucleophilic addition of secondary phosphine chalcogenides to the vinyl sulfoxides (∼50 mol% KOH, dioxane, 25–40°C, 1 h) followed by the elimination of sulfenic acids from the adducts (additional equivalent of KOH, 60–70°C, 1.5–2.0 h), the yields of target tertiary vinyl phosphine chalcogenides reaching 92%.

Reaction of secondary phosphine chalcogenides with 2,2,2-trichloroacetaldehyde

The nucleophilic addition of secondary phosphine chalcogenides to 2,2,2-trichloroacetaldehyde proceeds under mild noncatalytic conditions (12–25dgC, 15–90 min) with the formation of functional tertiary phosphine chalcogenides, containing hydroxy groups in up to 98% yield. Using the method of concurrent reactions the reactivity of secondary phosphine chalcogenides in this reaction was shown to decrease in the order: (PhCH2CH2)2P(O)H ≫ (PhCH2CH2)2P(S)H > (PhCH2CH2)2P(Se)H, and the secondary bis[2-(2-pyridyl) ethyl]-phosphine oxide was more reactive than bis(2-phenethyl)phosphine oxide.

ChemInform Abstract: Nucleophilic Addition of Secondary Phosphine Chalcogenides to α,β‐Acetylenic γ‐Hydroxy Acid Nitriles and a Rearrangement of the Adducts.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Nucleophilic addition of secondary phosphine chalcogenides to, α,β-acetylenic γ-hydroxy acid nitriles and a rearrangement of the adducts

Bis(2-phenylethyl)phosphine oxide and sulfide and bis[2-(2-pyridyl)ethyl]phosphine sulfide add easily (LiOH–THF, 28–30 °C) to 4-hydroxy-4-methyl-2-pentynenitrile to give regio- and stereoselectively 3-substituted ( Z )-4-hydroxy-4-methyl-2-pentenenitriles in 82–91% yield; the latter, upon heating (58–60 °C) in the presence of LiOH in THF, rearrange cleanly to the corresponding 3-cyano-2-propen-1-yl phosphinates and phosphinothioates (isolated yields of 82–86%).

Base Catalyzed Double Addition of Secondary Phosphine Chalcogenides to Benzoylacetylene

Secondary phosphine chalcogenides add to benzoylacetylene in KOH-THF suspension (the addition proceeds solely to the triple bond) to form depending on the PH-addend nature and reaction conditions either α,β- or β,β-diadducts, regardless of reactant ratio.

Chemoselective noncatalytic addition of secondary phosphine chalcogenides to citral

Addition of secondary phosphine oxides, phosphine sulfides and phosphine selenides to 3,7-dimethyl-2,6-octadienal (citral) (48–50°C, THF, argon) proceeds exclusively to the aldehyde group giving rise to new polyfunctional tertiary phosphine chalcogenides with diene and hydroxyl moieties in high preparative yield (up to 80%).