- Phosphinoyl and thiophosphinoylcarbodithioates: Synthesis, molecular structure, and application as new efficient mediators for RAFT polymerization
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New phosphinoyl and thiophosphinoylcarbodithioates were synthesized in a one-pot reaction from the corresponding phosphinochalcogenides. Compounds of this new generation of thiocarbonylthio derivatives have been fully characterized by IR as well as 1
- Mazires, Stphane,Kulai, Ihor,Geagea, Roland,Ladeira, Sonia,Destarac, Mathias
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- A structural and theoretical study of the thiophosphinite and dithiophosphinate anions
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Two novel lithium compounds containing either the phosphorus-chalcogenide anions [Ph2PS]- or [Cy2PS2]- were isolated as decomposition products in the attempted formation of phospha(V)guanidinate anions. Lithium diphenylthiophosphinite was structurally cha
- Mansfield, Natalie E.,Coles, Martyn P.,Hitchcock, Peter B.
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- Metal-free SHNcross-coupling of pyridines with phosphine chalcogenides: polarization/deprotonation/oxidation effects of electron-deficient acetylenes
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Terminal acylacetylenes, typical electron-deficient acetylenes, drive SHNcross-coupling of pyridines with secondary phosphine chalcogenides under metal-free mild conditions (20-75 °C) to afford 4-chalcogenophosphorylpyridines in up to 70% yield. The reaction proceedsvia2,4-migration of chalcogenophosphoryl groups in the intermediate 1-acylvinyl-2-phosphoryl dihydropyridines with simultaneous redox elimination of the vinyl ketone oligomers. These results are generalized in a concept of trimodal (polarization/deprotonation/oxidation) catalyst-like assistance of electron-deficient acetylenes in SHNreaction of the pyridinoid heterocycles with PH-nucleophiles, which comprises: (i) repolarization (umpolung) of the pyridine ring, (ii) deprotonation of secondary phosphine chalcogenides to generate phosphorus-centered anions and (iii) oxidation of the dihydro intermediates.
- Volkov, Pavel A.,Telezhkin, Anton A.,Khrapova, Kseniya O.,Ivanova, Nina I.,Albanov, Alexander I.,Gusarova, Nina K.,Trofimov, Boris A.
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p. 6206 - 6219
(2021/04/16)
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- Metal-free site selective cross-coupling of pyridines with secondary phosphine chalcogenides using acylacetylenes as oxidants
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Pyridines undergo site selective cross-coupling with secondary phosphine chalcogenides (oxides, sulfides, and selenides) in the presence of acylphenylacetylenes under metal-free mild conditions (70-75 °C, MeCN) to afford 4-chalcogenophosphoryl pyridines in up to 71% yield. In this new type of SNHAr reaction acylacetylenes act as oxidants, being stereoselectively reduced to the corresponding olefins of the E-configuration.
- Trofimov, Boris A.,Volkov, Pavel A.,Khrapova, Kseniya O.,Telezhkin, Anton A.,Ivanova, Nina I.,Albanov, Alexander I.,Gusarova, Nina K.,Chupakhin, Oleg N.
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supporting information
p. 3371 - 3374
(2018/04/05)
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- Synthesis of Phosphine Chalcogenides Under Solvent-Free Conditions Using a Rotary Ball Mill
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The mechanochemical technique of ball milling has been applied to the solventless and eco-friendly synthesis of chalcogenides (sulfide and selenide) of a variety of tertiary and aminophosphines. In most of the cases, the products are obtained in almost quantitative yields with high purity by applying a simple workup procedure without using chromatographic techniques or any other purification methods. The scope of this methodology was explored by using a range of phosphines (mono, di and tetra) to synthesize partial as well as mixed chalcogenides. The use of almost equimolar amounts of starting materials and the absence of any byproducts significantly simplifies the product isolation compared with the standard solution state reactions, thus providing a highly atom economic (100 %) method with an ideal E-factor (E = 0). The solid-state reactions were monitored by 31P{1H} NMR spectroscopy. The structures of some of the products are also confirmed by single-crystal X-ray analyses. Although most of the reactions were carried out on ca. 100-mg scale, the scaling up of the reaction did not affect the course of the reaction.
- Kumar, Rajnish,Kumar, Saurabh,Pandey, Madhusudan K.,Kashid, Vitthalrao S.,Radhakrishna, Latchupatula,Balakrishna, Maravanji S.
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p. 1028 - 1037
(2018/02/26)
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- Diastereoselective synthesis of N-sulfinyl α-aminophosphine sulfides and phosphines
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The diastereoselective synthesis of N-sulfinyl α-aminophosphine sulfides and phosphines is reported. These molecules are synthesized by formation of sulfinyl imine followed by diastereoselective addition of a diphenylphosphine sulfide. The product N-sulfinyl α-aminophosphine sulfides can be converted to phosphines through removal of the sulfur by reaction with Raney nickel. Hydrolysis of the sulfinyl group provides an amine that can then be attached to other ligands or structural scaffolds.
- Zhang, Wei,Gilbertson, Scott R.
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supporting information
p. 2175 - 2177
(2017/05/16)
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- Non-catalyzed addition of secondary phosphine chalcogenides to divinyl chalcogenides under solvent-free conditions
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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 cata
- Gusarova, Nina K.,Chernysheva, Nataliya A.,Yas’ko, Svetlana V.,Klyba, Lyudmila V.,Trofimov, Boris A.
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p. 488 - 500
(2016/10/03)
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- Green synthesis of tertiary alkylselanylphosphine chalcogenides via catalyst-and solvent-free addition of secondary phosphine chalcogenides to vinyl selenides
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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.
- Gusarova,Chernysheva,Yas'Ko,Trofimov
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p. 526 - 534
(2015/10/19)
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- An expedient access to γ-ketophosphine chalcogenides via the chemo-and regioselective addition of secondary phosphine chalcogenides to β,γ-ethylenic ketones
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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 so
- Artem’Ev, Alexander V.,Malysheva, Svetlana F.,Belogorlova, Nataliya A.,Protzuk, Nadezhda I.,Albanov, Alexander I.,Bagryanskaya, Irina Y.,Schmidt, Elena Y.,Gusarova, Nina K.,Trofimov, Boris A.
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p. 455 - 462
(2018/01/18)
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- Facile non-catalyzed synthesis of tertiary phosphine sulfides by regioselective addition of secondary phosphine sulfides to alkenes
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An 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, vin
- Malysheva, Svetlana F.,Gusarova, Nina K.,Artem'Ev, Alexander V.,Belogorlova, Nataliya A.,Albanov, Alexander I.,Borodina, Tatyana N.,Smirnov, Vladimir I.,Trofimov, Boris A.
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supporting information
p. 2516 - 2521
(2014/05/06)
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- Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with secondary phosphine sulfides: Synthesis of adducts
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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 C, 2.5 h, THF, reactants molar ratio = 1:1) to afford the ant
- Gusarova, Nina K.,Chernysheva, Nataliya A.,Klyba, Lyudmila V.,Shagun, Vladimir A.,Yas'Ko, Svetlana V.,Smirnov, Vladimir I.,Trofimov, Boris A.
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p. 126 - 132
(2013/10/01)
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- One-pot synthesis of ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides
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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.
- Gusarova, Nina K.,Kuimov, Vladimir A.,Malysheva, Svetlana F.,Belogorlova, Nataliya A.,Albanov, Alexander I.,Trofimov, Boris A.
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supporting information
p. 9218 - 9225
(2012/11/07)
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- A facile atom-economic synthesis of imidazoles with chalcogenophosphoryl substituents via free-radical addition of secondary phosphine chalcogenides to 1-vinylimidazoles
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Secondary phosphine sulfides and selenides react with 1-vinylimidazoles under radical initiation conditions to give the corresponding anti-Markovnikov adducts in up to 98% yields. Georg Thieme Verlag Stuttgart - New York.
- Gusarova, Nina K.,Malysheva, Svetlana F.,Belogorlova, Nataliya A.,Parshina, Lidiya N.,Trofimov, Boris A.
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experimental part
p. 1777 - 1782
(2011/07/06)
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- Radical addition reactions of phosphorus hydrides: Tuning the reactivity of phosphorus hydrides, the use of microwaves and horner-wadsworth-emmons-type reactions
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The reactivity of phosphorus hydrides in radical addition reactions are compared, and the substituents on phosphorus are shown to affect the efficiency of the reactions. The change in reactivity is attributed to the different bond dissociation energies of the P-H bonds, which have been calculated. Phosphorus hydrides with particularly weak P-H bonds are shown to undergo radical additions by microwave irradiation, in the absence of conventional initiators. These radical addition reactions produce phosphonothioates, phosphinothioates and phosphane sulfides, which react in HWE-type reactions, to afford substituted alkenes. copy; Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Jessop, Christopher M.,Parsons, Andrew F.,Routledge, Anne,Irvine, Derek J.
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p. 1547 - 1554
(2007/10/03)
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- Radical addition reactions of diphenylphosphine sulfide
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Radical additions of diphenylphosphine sulfide [Ph2P(S)H] to various C=C bonds offers a general, mild and efficient approach to alkyl(diphenyl)phosphine sulfides. Georg Thieme Verlag Stuttgart.
- Parsons, Andrew F.,Sharpe, David J.,Taylor, Philip
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p. 2981 - 2983
(2007/10/03)
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- Reductive cleavage of the halogen-phosphorus and sulfur-phosphorus bonds with alkali metals
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The reduction of thiophosphorus acid chlorides with alkali metals (Na, K) in liq. NH3/THF solution, potassium anthracenide, and potassium napththalenide was investigated. It was found that these types of phosphorus compounds easily undergo reduction to 〉P-S- anions. It was also demonstrated that 〉P-O- and 〉P-S- anions as well very efficiently undergo sulfurization with elementary sulfur in liquid ammonia to yield 〉P(O)S- and 〉P(S)S- anions, respectively.
- Stankiewicz, Marek,Nycz, Jacek,Rachon, Janusz
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p. 330 - 339
(2007/10/03)
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- Dual Radical/Polar Pudovik Reaction: Application Field of New Activation Methods
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The Pudovik reaction (addition of organophosphorus compounds containing a labile P-H bond with alkenes and alkynes) can progess via a radical or (and) ionic mechanism. A comparative and systematic study including various reagents and different activation methods (heating, photochemical or ultrasonic irradiation, and dry medium supported reactions) is presented. Photolysis is the most efficient method for the radical processes, but in a few examples, ultrasonic irradiation can be more appropriate since the reaction time is shorter and ultrasound did not induce side-reactions (in particular Z/E isomerization). Dry medium process on basic solid support is the best anionic activation (yield, time, selectivity, purification facilities). Ultrasound, by its mechanical effects, can contribute to increase yield compared to the classical thermal method under these basic conditions. All the activation methods are efficient whatever the unsaturated substrates for the phosphine reactivity, whereas the appropriate activation method is exclusively determined by the nature of the unsaturated system for the thiophosphine (or phosphine oxide) reactivity.
- Semenzin, Delphine,Etemad-Moghadam, Guita,Albouy, Dominique,Diallo, Ousmane,Koenig, Max
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p. 2414 - 2422
(2007/10/03)
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- ELECTROCHEMICAL REACTIONS OF PHOSPHORIC ACID DERIVATIVES. II. REDUCTION OF DIORGANYLPHOSPHINOUS DERIVATIVES
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The mechanism of the heterogenous reduction of diorganylphosphinous derivatives includes the stages of electron transfer, breakage of the P-El (El = S, C) bond in the radical anion, and subsequent chemical reaction between the phosphide anion and the original molecule.Examination of the homogeneous reduction of diorganylphosphinous derivatives with help of electrochemically generated radical anions as mediators shows that the kinetic characteristics of the separate stages of the process depend strongly on the nature of the mediator, and in some cases the mediator affects the nature of the product.Thus, the reduction of Ph2PSBu by the radical anion of anthracene gives the diphosphide, while the radical anion of bipyridine leads to the isomerization product Ph2P(S)Bu.It is suggested that the electron transfer has inner-sphere character, that between the mediator and the substrate a complex is formed, and that this determines the whole mechanism of the reduction.
- Budnikova, Yu. G.,Novoselova, T. R.,Kargin, Yu. M.
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p. 1267 - 1273
(2007/10/02)
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- Reactions of P_Cl compounds in presence of SMI2
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Conversion of P-Cl to P-H and P-C bonds are induced by SmI2 in mild conditions. Especially phosphines oxides and sulfides are obtained in good yields.
- Sasaki, Mitsuru,Collin, Jacqueline,Kagan, Henri B.
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p. 2493 - 2496
(2007/10/02)
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- NOVEL ANIONIC CHALCOGENO LIGANDS. TELLUROPHOSPHINITES R2PTe- AND CHALCOGENOTELLUROPHOSPHINATES R2P(Ch)Te-
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Elemental tellurium reacts with diorganylphosphides R2P- to give tellurophosphinites R2PTe- and with chalcogenophosphinites R2PCh- to give chalcogenotellurophosphinates R2P(Ch)Te- R = C6H11, C6H5; Ch = O,S,Se,T
- Bildstein, Benno,Sladky, Fritz
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p. 341 - 347
(2007/10/02)
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