Phosphine Sulfide Research Articles

Reliable Synthesis of Phosphino‐ and Phosphine Sulfide‐1,2,3,4‐Tetrahydroquinolines and Phosphine Sulfide Quinolines

The synthesis of phosphino‐ and phosphine sulfide‐1,2,3,4‐tetrahydroquinolines and phosphine sulfide quinolines is described. The synthetic route involves a multicomponent reaction of 2‐phosphinoaniline or 2‐phosphine sulfide‐aniline, aldehydes, and styrenes for the preparation of phosphino‐ or phosphine sulfide‐1,2,3,4‐tetrahydroquinolines and allows for the selective generation of two stereogenic centers in a short, efficient, and reliable approach. The selective oxidation of phosphine sulfide‐1,2,3,4‐tetrahydroquinolines led to the formation of the phosphine sulfide quinolines.

Triphosphasumanene Trisulfide: High Out-of-Plane Anisotropy and Janus-Type π-Surfaces

A triphosphasumanene trisulfide was designed and synthesized as an out-of-plane anisotropic π-conjugated molecule. Incorporating three anisotropic phosphine sulfide moieties into a sumanene skeleton induced a cumulative anisotropy with a large dipole moment (12.0 D), which is aligned in perpendicular direction with respect to the π-framework and more than twice as large as those of conventional out-of-plane anisotropic molecules. In the crystal, the molecules align to form columnar structures, in which electron-rich and electron-deficient sides of the π-framework face each other. The interactions between the electron-rich surfaces, which contain three sulfur atoms, and Au(111) were examined by X-ray photoelectron spectroscopy.

Raney-Ni reduction of phosphine sulfides

GRAPHICAL ABSTRACT

The Catalyst-Controlled Regiodivergent Chlorination of Phenols.

Different catalysts are demonstrated to overcome or augment a substrate's innate regioselectivity. Nagasawa's bis-thiourea catalyst was found to overcome the innate para-selectivity of electrophilic phenol chlorination, yielding ortho-chlorinated phenols that are not readily obtainable via canonical electrophilic chlorinations. Conversely, a phosphine sulfide derived from 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) was found to enhance the innate para-preference of phenol chlorination.

ChemInform Abstract: Practical Way for the Synthesis of Phosphine Oxides and Phosphine Sulfides from Benzyl Alcohol Derivatives.

AbstractPentavalent phosphorus compounds are prepared by reaction of various benzyl alcohols with Ph2PI in situ generated from Ph2PCl and NaI.

Zirconium-Catalyzed Reactions of 1-Alkynyl Phosphine Oxides and Sulfides with Et3Al

The interaction of 1-alkynyl phosphine oxides, sulfides, and selenides with Me 3 Al and Et 3 Al under zirconocene catalysis was studied. It has been found that the pathway of the reaction of 1-alkynyl phosphine derivatives with Et 3 Al strongly depends on the nature of the substrate and the solvent. The ethylalumination takes place in the case of 1-alkynyl phosphine oxides in hexane solvent. The reaction of 1-hexynyl phosphine oxide with Et 3 Al failed when dichloromethane was used as a solvent. Zirconium-catalyzed reaction of 1-heptynyl phosphine sulfide with Et 3 Al proceeds as the cycloalumination followed by the desulfurization under the action of low-valent zirconium complexes. 1-Heptynyl phosphine selenide was subjected to full deselenation under the reaction conditions.

ChemInform Abstract: Straightforward Solvent‐Free Synthesis of Tertiary Phosphine Chalcogenides from Secondary Phosphines, Electron‐Rich Alkenes, and Elemental Sulfur or Selenium.

A series of tertiary phosphine sulfides and selenides have been synthesized in excellent yields (88-99%) via a three-component reaction between secondary phosphines, electron-rich alkenes (styrene, vinyl chalcogenides), and elemental sulfur or selenium, proceeding under solvent-free conditions (80-82°C, 4–44 h). The interaction occurs via initial oxidation of secondary phosphines with elemental sulfur or selenium followed by noncatalyzed anti-Markovnikov addition of the generated R2P(E)H (E = S, Se) species to alkenes to afford the corresponding adducts with high chemo- and regioselectivity.

Practical way for the synthesis of phosphine oxides and phosphine sulfides from benzyl alcohol derivatives

The reaction of benzyl alcohol derivatives with Ph2PI generated in situ from Ph2PCl and NaI provides a facile way to the synthesis of pentavalent phosphine compounds with moderate to excellent yields.

Kinetic Resolution of Planar-Chiral Ferrocenylphosphine Derivatives by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis and Their Application in Asymmetric Catalysis

Highly enantioselective kinetic resolution of racemic planar-chiral metallocenylphosphine sulfides was realized by the molybdenum-catalyzed asymmetric ring-closing metathesis reaction with the krel values of up to 147. The enantiomerically enriched 1,4-but-2-enylene-bridged ferrocenylphosphine sulfides thus obtained could be purified to enantiomerically pure forms by simple recrystallization from hot methanol, and subsequent reduction of the phosphine sulfides provided the corresponding planar-chiral phosphines with retention of the enantiomeric homogeneity. This is a rare example of preparing planar-chiral ferrocenylphosphines by catalytic asymmetric reactions. The single-enantiomer planar-chiral ferrocenylphosphines were applied as chiral ligands in the rhodium-catalyzed asymmetric 1,4-addition reaction (the Hayashi–Miyaura conjugate addition reaction) of phenylboronic acid to 2-cyclohexenone to show excellent enantioselectivity and high yields. The NMR studies clarified that the butenylene-bridged ferr...

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.

The synthesis and efficient one-pot catalytic "self-breeding" of asymmetrical NC(sp(3))E-hybridised pincer complexes.

Cyclopalladation of the pyridyl-substituted chiral phosphine sulfide (N-P=S) and oxide (N-P=O) compounds afforded the asymmetric N-C(sp(3))*-S and N-C(sp(3))*-O pincer complexes. When applied as catalysts in asymmetric hydrophosphination, the newly developed aliphatic pincer catalyst could be recycled over three runs and obtained in large quantities via a one-pot "self-breeding" catalytic protocol.

Straightforward Solvent‐Free Synthesis of Tertiary Phosphine Chalcogenides from Secondary Phosphines, Electron‐Rich Alkenes, and Elemental Sulfur or Selenium

ABSTRACTA series of tertiary phosphine sulfides and selenides have been synthesized in excellent yields (88‐99%) via a three‐component reaction between secondary phosphines, electron‐rich alkenes (styrene, vinyl chalcogenides), and elemental sulfur or selenium, proceeding under solvent‐free conditions (80‐82°C, 4–44 h). The interaction occurs via initial oxidation of secondary phosphines with elemental sulfur or selenium followed by noncatalyzed anti‐Markovnikov addition of the generated R2P(E)H (E = S, Se) species to alkenes to afford the corresponding adducts with high chemo‐ and regioselectivity.

Gold and Silver Chains Supported by Linear Hexaphosphine Ligands.

A new linear hexaphosphine, rac-cis,cis,trans-bis{[(diphenylphosphinomethyl)phenylphosphinomethyl]phenylphosphino}methane (P6), was synthesized and isolated as a pure isomer, confirmed by transforming to the corresponding phosphine sulfide. The methylene-bridged linear hexaphosphine readily organized flexible gold(I) and silver(I) hexanuclear chains, [M6(μ-P6)2]X6 (X6 = (OTf)6, M = Au (1), Ag (2); X6 = Cl2(PF6)4, M = Au (3)). The hexaphosphine also supported a tetrasilver(I) complex [Ag4(μ-P6)2](OTf)4 (4), which was readily transformed by treatment with AgOTf into 3, revealing a drastic alternation of the two P6 arrangement. The hexagold(I) chains exhibited a considerably red-shifted absorption (∼410 nm) and emission (540-580 nm) to (1) [5dσ*→6pσ] and from (3) [5dσ*→6pσ] excited states of the metal centers, respectively. The new linear hexaphosphine could be a useful tool to construct linear metal clusters as subnano building blocks.

Calorimetric and Potentiometric Studies of Ag+ Complexation With Tris(Dimethylamino)Phosphine Sulfide in Acetonitrile Solution

GRAPHICAL ABSTRACT

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.

Synthesis, spectroscopy, electrochemistry, and coordination chemistry of substituted phosphine sulfides and selenides

Phosphines and phosphine chalcogenides are important ligands for various metal systems, especially catalysts. Based on previously synthesized phosphine oxide ligands, we describe here the synthesis and characterization of a series of compounds having the general formula, EPPh2Ar, E=S, Se; Ar=1-naphthyl, 9-phenanthryl, 9-anthracenyl, 1-pyrenyl. Reaction of EPPh2(9-phenanthryl), E=S, Se, with HAuCl4 yields ArPh2PEAuCl. Similar to the phosphine oxide derivative, the anthracenyl compounds, EPPh2(9-anthracenyl), showed a nonplanar conformation within the anthracene ring as observed using X-ray crystallography. The difference in fluorescence spectrum relative to the parent aryl species is attributed to this deformation. The deviation is probably due to steric strain within the phosphine ligand due to its position on the anthracenyl ring since DFT calculations suggest that the 1-anthracenyl ligand should be planar. Each compound has been characterized using 1H, 13C, 31P, and (where applicable) 77Se NMR, and IR spectroscopy, with structure determination by X-ray crystallography. Finally, the electrochemistry of the unoxidized phosphines is reported, showing one-electron reductions in the polycyclic aromatic hydrocarbons.

ChemInform Abstract: Air‐Stable Palladium(0) Phosphine Sulfide Catalysts for Ullmann‐Type C—N and C—O Coupling Reactions.

AbstractPhenyl bromide as reaction partner in amination and etherification gives similar (amination) or lower (etherification) yields at longer reaction times.

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.

Highly efficient reduction of tertiary phosphine oxides and sulfides with amine-assisted aluminum hydrides under mild conditions

Reduction of tertiary phosphine oxides and sulfides into the corresponding phosphines with amine-assisted aluminum hydrides has been studied. The method is characterized by mild conditions, short reaction time, high efficiency, and expanded substrate scope. The new method is an alternative to the currently used methods of reducing phosphine oxides or recycling phosphines engaged in organic reactions.

A practical Lewis base catalyzed electrophilic chlorination of arenes and heterocycles.

A mild phosphine sulfide catalyzed electrophilic halogenation of arenes and heterocycles that utilizes inexpensive and readily available N-halosuccinimides is disclosed. This methodology is shown to efficiently chlorinate diverse aromatics, including simple arenes such as anthracene, and heterocycles such as indoles, pyrrolopyrimidines, and imidazoles. Arenes with Lewis acidic moieties also proved amenable, underscoring the mild nature of this chemistry. Lewis base catalysis was also found to improve several diverse aromatic brominations and iodinations.