Secondary Phosphine Selenides Research Articles

Selenium Transfer from Secondary Phosphine Selenides to Aminoacetylenic Ketones: Access to 1,2-Dihydro-3H-pyrrole-3-selones with a Stable C═Se Bond.

Secondary phosphine selenides were found to react with γ-aminoacetylenic ketones (80-85 °C, MeCN, 17-40 h) to afford 1,2-dihydro-3H-pyrrole-3-selones in 48-80% yields, products of unprecedented selenium transfer from the P═Se bond to replace the carbonyl oxygen and to form dihydro-3H-pyrrole-3-selones having a C═Se bond stable under ambient conditions.

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.

Unexpected Carbon–Selenium Bond Formation in the Reaction of Secondary Phosphine Selenides with Benzoylphenylacetylene

Secondary phosphine selenides reacted as selenating agents with benzoylphenylacetylene in wet acetonitrile (70–72°C) to give bis(2-benzoyl-1-phenylvinyl) selenide in up to 43% yield.

Catalyst-free selenylation of acylacetylenes with secondary phosphine selenides and water: A short-cut to bis(2-acylvinyl) selenides

Secondary phosphine selenides react with acylacetylenes in water to form bis(2-acylvinyl) selenides. The reaction proceeds without catalyst and organic solvent under mild conditions (70–72 °C, 3 h), the corresponding divinyl selenides being isolated as a mixture of (Z,Z)- and (E,Z)-isomers in a yield of up to 78%.

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

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‐Free and Solvent‐Free Addition of P(Se)—H Species to Alkenes: A Straightforward Access to Tertiary Phosphine Selenides.

Under catalyst- and solvent-free conditions, secondary phosphine selenides easily add to diverse alkenes [acrylonitrile, allyl alcohol, styrene, vinyl ethers, vinyl sulfides, and trimethyl(vinyl)silane] at 80 °C (3–20 h) to give anti-Markovnikov adducts in 70–95% yield.

Dual reactivity of secondary phosphines and their chalcogenides towards 1-(vinyloxy)alkylferrocenes: the switch between α- and β-addition

The secondary phosphines and their sulfides regioselectively add, under free radical conditions (AIBN, 65 °C or UV-irradiation, rt), to (vinyloxy)methyl- and 1-(vinyloxy)ethylferrocenes to give anti-Markovnikov adducts in high yields. Without any initiator, the secondary phosphine selenides, when reacted with the above alkenes (rt, 24 h), selectively form Markovnikov adducts, which readily decompose upon handling to afford diorganyl[1-(ferrocenyl)alkyl]phosphine selenides, R2P(Se)CH(R′)Fc (R=Ph; R′=H or Me) in 28–39% isolated yields. The synthesized compounds were characterized using 1H, 13C, 31P NMR, and FTIR spectroscopy as well as X-ray diffraction analysis.

Catalyst-Free and Solvent-Free Addition of P(Se)–H Species to Alkenes: A Straightforward Access to Tertiary Phosphine Selenides

Under catalyst- and solvent-free conditions, secondary phosphine selenides easily add to diverse alkenes [acrylonitrile, allyl alcohol, styrene, vinyl ethers, vinyl sulfides, and trimethyl(vinyl)silane] at 80 °C (3–20 h) to give anti-Markovnikov adducts in 70–95% yield.

ChemInform Abstract: Cross‐Coupling Between Secondary Phosphine Selenides and Primary or Secondary Amines: Halogen‐Free Synthesis of Phosphinoselenoic Amides.

Secondary phosphine selenides react with primary or secondary amines at 60–65 °C in dioxane to give phosphinoselenoic amides.

ChemInform Abstract: Oxidative Cross‐Coupling Between Secondary Phosphine Selenides and Thiols or Dithiols: A Facile Regio‐Selective Synthesis of Thioselenophosphinic S‐Esters and S‐Diesters.

AbstractThe reaction is proposed to proceed via a secondary phosphine‐selenide free radical formed on treatment of the starting selenides with the NEt3/CCl4 oxidative system.

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.

Cross-coupling between secondary phosphine selenides and primary or secondary amines: halogen-free synthesis of phosphinoselenoic amides

Secondary phosphine selenides react with primary or secondary amines at 60–65 °C in dioxane to give phosphinoselenoic amides.

CuInSe2 Quantum Dot Solar Cells with High Open-Circuit Voltage.

CuInSe2 (CISe) quantum dots (QDs) were synthesized with tunable size from less than 2 to 7 nm diameter. Nanocrystals were made using a secondary phosphine selenide as the Se source, which, compared to tertiary phosphine selenide precursors, was found to provide higher product yields and smaller nanocrystals that elicit quantum confinement with a size-dependent optical gap. Photovoltaic devices fabricated from spray-cast CISe QD films exhibited large, size-dependent, open-circuit voltages, up to 849 mV for absorber films with a 1.46 eV optical gap, suggesting that midgap trapping does not dominate the performance of these CISe QD solar cells.

Oxidative cross-coupling between secondary phosphine selenides and thiols or dithiols: a facile regio-selective synthesis of thioselenophosphinic S-esters and S-diesters

Abstract Reactions between secondary phosphine selenides and a wide range of aliphatic, aromatic and heteroaromatic thiols or dithiols proceed in the Et 3 N/CCl 4 oxidative system under mild conditions (rt 1–3 h) to give thioselenophosphinic S -esters or S -diesters in 80–92% isolated yields.

Polarity and Conformational Analysis of Secondary Phosphine Selenides

The polarities of bis(2-phenylethyl) and bis(2-phenylpropyl) phosphine selenides were determined and conformational analysis of these phosphine selenides was carried out by the method of dipole moments, IR spectroscopy, and quantum chemical calculations. They exist as an equilibrium of several conformers, and the preferred conformers have gauche orientation of the P = Se and Csp3 – Csp3 bonds.

One-pot synthesis of ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides

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.

ChemInform Abstract: A Simple One‐Pot Synthesis of Phosphinoselenoic Amides and Diamides from Secondary Phosphine Selenides and Amines Using Et3N—CCl4.

Abstract The multi-component reaction between secondary phosphine selenides and amines (primary, secondary, and primary diamines) proceeds using the Et 3 N-CCl 4 system under mild conditions to give phosphinoselenoic amides or diamides in 81–89% isolated yields.