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Boris A. Trofimov - One of the best experts on this subject based on the ideXlab platform.
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Aerobic addition of Secondary Phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl- (diorganyl)Phosphine oxides
2020Co-Authors: Svetlana F Malysheva, Boris A. Trofimov, Nina K. Gusarova, A I Albanov, Nataliya A Belogorlova, Alexander V Artem&apos, C W LiuAbstract:Abstract Secondary Phosphine oxides react with vinyl sulfides (both alkyl-and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7-30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides in 70-93% yields. Findings Tertiary Phosphines and Phosphine chalcogenides are important organophosphorus compounds that are widely used in industry, organic synthesis, polymer science, medicinal and coordination chemistry Recently, on example of Secondary Phosphines [27] as well as Secondary Phosphine sulfides In this letter, we report our serendipitous finding that Secondary Phosphine oxides 1a-f under aerobic conditions (air, 80 °C, 7-18 h) easily add to vinyl sulfides 2a-c to give unknown 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides 3a-h in high yields Importantly, under these conditions, the expected [30] antiMarkovnikov adducts are not observed in detectable amounts ( 31 P NMR). The main byproducts are phosphinic acids, R 2 P(O)OH, formed by air oxidation of Secondary Phosphine oxides 1a-f. As seen from The presence of an asymmetric carbon atom in the reaction products leads to non-equivalence of both heminal protons in the SCH 2 C* fragment and carbon signals in the arylethyl moiety. In the 1 H NMR spectra of 3a-h, protons of the PCHCH 2 S moiety form an ABMX spin system appearing as three multiplets. Phosphine oxide 3d crystallizes in the centrosymmetric P2 1 /c space group. Within its extended structure, strong intermolecular H-bonding interactions between the O-H hydrogen and P=O oxygen atom of a second molecule {O(1)-H(1)···O(2), 1.80(6) Å; O-H···O angle, 174.9(7)°} leads to the formation of 1D polymeric chains along the b-axis ( In FTIR spectra of 3a-h, absorption bands of the P=O and O-H bonds appear in the regions of 1100-1150 and 3350-3450 cm −1 , respectively. Interestingly, the reaction disclosed is specific for Secondary Phosphine oxides. Our experiments have shown that their analogues, Secondary Phosphine sulfides, under similar conditions provide exclusively the anti-Markovnikov adducts (Scheme 2). On the other hand, vinyl ethers and vinyl selenides Beilstein J. Org. Chem. 2015, 11, 1985-1990. 1988 Figure 1: ORTEP drawing (30% thermal ellipsoid) of Phosphine oxide 3d. A CIF file with the crystallographic data is available as Supporting Information File 2 and is also available on request from the Cambridge Crystallographic Data Centre as deposition 1046604. (congeners of vinyl sulfides) were found to react with Phosphine oxide 1a at 80 °C for about 30 and 20 h, respectively, to deliver difficult-to-separate mixtures of organophosphorus compounds ( 31 P NMR). Scheme 2: Addition of Secondary Phosphine sulfide to vinyl sulfide under aerobic catalyst-free conditions. To gain a primary insight into the reaction mechanism, several experiments were carried out. On example of Phosphine oxide 1a and vinyl sulfide 2c, we have shown that the reaction proceeds in the dark with the same efficiency as in the light. Therefore, the photochemical pathway of the reaction is hardly probable. Also, the reaction was established under an argon atmosphere. Under these conditions (argon, 80 °C for 18 h, exemplified by 1a/2c pair) the formation of products 3a-h does not take place and the starting Phosphine oxide remained almost intact ( 31 P NMR). This indicates that the reaction requires the presence of oxygen. In the other experiment, when TEMPO, a widely used radical scavenger, was added (10 mol %) into the reaction system 1a/2c, the product 3d was also formed, however, a longer reaction time was required for complete conversion of Secondary Phosphine oxide 1a as compared to TEMPO-free conditions (15 vs 11 h). Meanwhile, this observation does not completely exclude a radical mechanism since the cross-coupling reactions between TEMPO and radical intermediates can be reversible Taking these data into account, the following mechanism is suggested (Scheme 3). The first step is assumed to be the generation of phosphinoyl (A) and hydroperoxyl (HOO • ) radicals by the reaction of O 2 with Phosphine oxide 1. Earlier, the transfer of a hydrogen atom from the P(O)H species to molecular oxygen has been reported for example for Ph 2 P(O)H Although quantum chemical computations [MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p)] of the model radicals B and C (with R, R' = Me) reveals that the latter is energetically less preferred than the former, their energy difference is too small (4.38 kcal/mol) to completely prohibit the B→C transformation. Beilstein J. Org. Chem. 2015, 11, 1985-1990. 1989 Scheme 3: Putative mechanism. Conclusion In summary, we have disclosed an aerobic addition of Secondary Phosphine oxides to vinyl sulfides under solvent-and catalyst-free conditions, which provides an efficient approach to hitherto unknown 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides in one step. The synthesized Phosphine oxides, bearing hydroxy and sulfide functions, represent prospective building blocks for organic synthesis and interesting ligands for metal complexes. The results obtained contribute to the basic chemistry of both Phosphine oxides and vinyl sulfides
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metal free site selective cross coupling of pyridines with Secondary Phosphine chalcogenides using acylacetylenes as oxidants
Chemical Communications, 2018Co-Authors: Boris A. Trofimov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, Pavel A Volkov, A I Albanov, O N ChupakhinAbstract: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.
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Catalyst-Free Phosphorylation of Acridine with Secondary Phosphine Chalcogenides: Nucleophilic Addition vs SNHAr Reaction
2018Co-Authors: Pavel A. Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, A I Albanov, Nina I. Ivanova, Boris A. TrofimovAbstract:Acridine adds Secondary Phosphine chalcogenides HP(X)R2 (X = O, S, Se; R = Ar, ArAlk) under catalyst-free conditions at 70–75 °C (both in the presence and absence of the electron-deficient acetylenes) to give 9-chalcogenophosphoryl-9,10-dihydroacridines in 61–94% yields. This contrasts with pyridines, which under similar conditions undergo an SNHAr reaction, wherein electron-deficient acetylenes play the role of oxidants. For acridine, the SNHAr step has been accomplished by the oxidation of the intermediate 9-phosphoryl-9,10-dihydroacridines (X = O) with chloranil
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structural effect in the reductive vinylation phosphorylation of pyridines with alkyl propiolates and Secondary Phosphine chalcogenides protonation vs zwitterion generation
Mendeleev Communications, 2017Co-Authors: Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, Pavel A Volkov, A I Albanov, Boris A. TrofimovAbstract: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.
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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
ChemInform, 2016Co-Authors: Alexander V Artemev, Nina K. Gusarova, S F Malysheva, Irina Yu Bagryanskaya, A I Albanov, Nataliya A Belogorlova, Nadezhda I Protzuk, Elena Yu Schmidt, Boris A. TrofimovAbstract: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.
Nina K. Gusarova - One of the best experts on this subject based on the ideXlab platform.
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oxidative cross coupling of Secondary Phosphine chalcogenides with amino alcohols and aminophenols aspects of the reaction chemoselectivity
Organic and Biomolecular Chemistry, 2021Co-Authors: K. O. Khrapova, Nina K. Gusarova, L. I. Larina, A. A. Telezhkin, Pavel A Volkov, D V Pavlov, B A TrofimovAbstract:Secondary Phosphine chalcogenides react with primary amino alcohols under mild conditions (room temperature, molar ratio of the initial reagents 1 : 1) in a CCl4/Et3N oxidizing system to chemoselectively deliver amides of chalcogenophosphinic acids with free OH groups. Under similar conditions, mono-cross-coupling between Secondary Phosphine chalcogenides and 1,2- or 1,3-aminophenols proceeds only with the participation of phenolic hydroxyl to give aminophenylchalcogenophosphinic O-esters. The yields of the synthesized functional amides or esters are 60–85%.
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catalyst and solvent free hydrophosphorylation of ketones with Secondary Phosphine oxides green synthesis of tertiary α hydroxyPhosphine oxides
Synthesis, 2020Co-Authors: Nina K. Gusarova, L. I. Larina, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, Pavel A Volkov, D V Pavlov, Andrei V Afonin, B A TrofimovAbstract:Tertiary α-hydroxyPhosphine oxides have been synthesized via the catalyst- and solvent-free reaction between available Secondary Phosphine oxides and aliphatic, aromatic and heteroaromatic ketones at 20–62 °C in near to 96–98% yield. The developed method meets the requirements of green chemistry and the PASE (pot, atom, step economy) paradigm. According to quantum-chemical calculations at the B3LYP/6-311++G(d,p) level, the synthesized hydroxyPhosphine oxides feature a weak (≈3 kcal·mol–1) O−H···O=P intramolecular hydrogen bond.
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catalyst free regio and chemoselective addition of Secondary Phosphine oxides to isoquinolines
Russian Chemical Bulletin, 2020Co-Authors: Pavel A Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, A I Albanov, T I Vakulskaya, S S Khutsishvili, B A TrofimovAbstract:Isoquinolines react with Secondary Phosphine oxides without catalyst (70–75 °C, 10–15 h, without solvent or in MeCN) to chemo- and regioselectively form previously unknown diadducts, 1,3-bis(diorganylphosphoryl)-1,2,3,4-tetrahydroisoquinolines, in high yields (85–95%).
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Oxidative Cross-Coupling of Cysteamine with Secondary Phosphine Chalcogenides: Aspects of Reaction Chemoselectivity
Doklady Chemistry, 2020Co-Authors: K. O. Khrapova, Nina K. Gusarova, L. I. Larina, A. A. Telezhkin, P. A. Volkov, N. I. Ivanova, K. A. Apartsin, V. V. KireevaAbstract:Cysteamine (2-aminoethanethiol) undergoes oxidative cross-coupling with Secondary Phosphine sulfides and Phosphine selenides under mild conditions (room temperature, 2–5 h, CCl_4/Et_3N) 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.
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Aerobic addition of Secondary Phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl- (diorganyl)Phosphine oxides
2020Co-Authors: Svetlana F Malysheva, Boris A. Trofimov, Nina K. Gusarova, A I Albanov, Nataliya A Belogorlova, Alexander V Artem&apos, C W LiuAbstract:Abstract Secondary Phosphine oxides react with vinyl sulfides (both alkyl-and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7-30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides in 70-93% yields. Findings Tertiary Phosphines and Phosphine chalcogenides are important organophosphorus compounds that are widely used in industry, organic synthesis, polymer science, medicinal and coordination chemistry Recently, on example of Secondary Phosphines [27] as well as Secondary Phosphine sulfides In this letter, we report our serendipitous finding that Secondary Phosphine oxides 1a-f under aerobic conditions (air, 80 °C, 7-18 h) easily add to vinyl sulfides 2a-c to give unknown 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides 3a-h in high yields Importantly, under these conditions, the expected [30] antiMarkovnikov adducts are not observed in detectable amounts ( 31 P NMR). The main byproducts are phosphinic acids, R 2 P(O)OH, formed by air oxidation of Secondary Phosphine oxides 1a-f. As seen from The presence of an asymmetric carbon atom in the reaction products leads to non-equivalence of both heminal protons in the SCH 2 C* fragment and carbon signals in the arylethyl moiety. In the 1 H NMR spectra of 3a-h, protons of the PCHCH 2 S moiety form an ABMX spin system appearing as three multiplets. Phosphine oxide 3d crystallizes in the centrosymmetric P2 1 /c space group. Within its extended structure, strong intermolecular H-bonding interactions between the O-H hydrogen and P=O oxygen atom of a second molecule {O(1)-H(1)···O(2), 1.80(6) Å; O-H···O angle, 174.9(7)°} leads to the formation of 1D polymeric chains along the b-axis ( In FTIR spectra of 3a-h, absorption bands of the P=O and O-H bonds appear in the regions of 1100-1150 and 3350-3450 cm −1 , respectively. Interestingly, the reaction disclosed is specific for Secondary Phosphine oxides. Our experiments have shown that their analogues, Secondary Phosphine sulfides, under similar conditions provide exclusively the anti-Markovnikov adducts (Scheme 2). On the other hand, vinyl ethers and vinyl selenides Beilstein J. Org. Chem. 2015, 11, 1985-1990. 1988 Figure 1: ORTEP drawing (30% thermal ellipsoid) of Phosphine oxide 3d. A CIF file with the crystallographic data is available as Supporting Information File 2 and is also available on request from the Cambridge Crystallographic Data Centre as deposition 1046604. (congeners of vinyl sulfides) were found to react with Phosphine oxide 1a at 80 °C for about 30 and 20 h, respectively, to deliver difficult-to-separate mixtures of organophosphorus compounds ( 31 P NMR). Scheme 2: Addition of Secondary Phosphine sulfide to vinyl sulfide under aerobic catalyst-free conditions. To gain a primary insight into the reaction mechanism, several experiments were carried out. On example of Phosphine oxide 1a and vinyl sulfide 2c, we have shown that the reaction proceeds in the dark with the same efficiency as in the light. Therefore, the photochemical pathway of the reaction is hardly probable. Also, the reaction was established under an argon atmosphere. Under these conditions (argon, 80 °C for 18 h, exemplified by 1a/2c pair) the formation of products 3a-h does not take place and the starting Phosphine oxide remained almost intact ( 31 P NMR). This indicates that the reaction requires the presence of oxygen. In the other experiment, when TEMPO, a widely used radical scavenger, was added (10 mol %) into the reaction system 1a/2c, the product 3d was also formed, however, a longer reaction time was required for complete conversion of Secondary Phosphine oxide 1a as compared to TEMPO-free conditions (15 vs 11 h). Meanwhile, this observation does not completely exclude a radical mechanism since the cross-coupling reactions between TEMPO and radical intermediates can be reversible Taking these data into account, the following mechanism is suggested (Scheme 3). The first step is assumed to be the generation of phosphinoyl (A) and hydroperoxyl (HOO • ) radicals by the reaction of O 2 with Phosphine oxide 1. Earlier, the transfer of a hydrogen atom from the P(O)H species to molecular oxygen has been reported for example for Ph 2 P(O)H Although quantum chemical computations [MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p)] of the model radicals B and C (with R, R' = Me) reveals that the latter is energetically less preferred than the former, their energy difference is too small (4.38 kcal/mol) to completely prohibit the B→C transformation. Beilstein J. Org. Chem. 2015, 11, 1985-1990. 1989 Scheme 3: Putative mechanism. Conclusion In summary, we have disclosed an aerobic addition of Secondary Phosphine oxides to vinyl sulfides under solvent-and catalyst-free conditions, which provides an efficient approach to hitherto unknown 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides in one step. The synthesized Phosphine oxides, bearing hydroxy and sulfide functions, represent prospective building blocks for organic synthesis and interesting ligands for metal complexes. The results obtained contribute to the basic chemistry of both Phosphine oxides and vinyl sulfides
A I Albanov - One of the best experts on this subject based on the ideXlab platform.
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catalyst free regio and chemoselective addition of Secondary Phosphine oxides to isoquinolines
Russian Chemical Bulletin, 2020Co-Authors: Pavel A Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, A I Albanov, T I Vakulskaya, S S Khutsishvili, B A TrofimovAbstract:Isoquinolines react with Secondary Phosphine oxides without catalyst (70–75 °C, 10–15 h, without solvent or in MeCN) to chemo- and regioselectively form previously unknown diadducts, 1,3-bis(diorganylphosphoryl)-1,2,3,4-tetrahydroisoquinolines, in high yields (85–95%).
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Aerobic addition of Secondary Phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl- (diorganyl)Phosphine oxides
2020Co-Authors: Svetlana F Malysheva, Boris A. Trofimov, Nina K. Gusarova, A I Albanov, Nataliya A Belogorlova, Alexander V Artem&apos, C W LiuAbstract:Abstract Secondary Phosphine oxides react with vinyl sulfides (both alkyl-and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7-30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides in 70-93% yields. Findings Tertiary Phosphines and Phosphine chalcogenides are important organophosphorus compounds that are widely used in industry, organic synthesis, polymer science, medicinal and coordination chemistry Recently, on example of Secondary Phosphines [27] as well as Secondary Phosphine sulfides In this letter, we report our serendipitous finding that Secondary Phosphine oxides 1a-f under aerobic conditions (air, 80 °C, 7-18 h) easily add to vinyl sulfides 2a-c to give unknown 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides 3a-h in high yields Importantly, under these conditions, the expected [30] antiMarkovnikov adducts are not observed in detectable amounts ( 31 P NMR). The main byproducts are phosphinic acids, R 2 P(O)OH, formed by air oxidation of Secondary Phosphine oxides 1a-f. As seen from The presence of an asymmetric carbon atom in the reaction products leads to non-equivalence of both heminal protons in the SCH 2 C* fragment and carbon signals in the arylethyl moiety. In the 1 H NMR spectra of 3a-h, protons of the PCHCH 2 S moiety form an ABMX spin system appearing as three multiplets. Phosphine oxide 3d crystallizes in the centrosymmetric P2 1 /c space group. Within its extended structure, strong intermolecular H-bonding interactions between the O-H hydrogen and P=O oxygen atom of a second molecule {O(1)-H(1)···O(2), 1.80(6) Å; O-H···O angle, 174.9(7)°} leads to the formation of 1D polymeric chains along the b-axis ( In FTIR spectra of 3a-h, absorption bands of the P=O and O-H bonds appear in the regions of 1100-1150 and 3350-3450 cm −1 , respectively. Interestingly, the reaction disclosed is specific for Secondary Phosphine oxides. Our experiments have shown that their analogues, Secondary Phosphine sulfides, under similar conditions provide exclusively the anti-Markovnikov adducts (Scheme 2). On the other hand, vinyl ethers and vinyl selenides Beilstein J. Org. Chem. 2015, 11, 1985-1990. 1988 Figure 1: ORTEP drawing (30% thermal ellipsoid) of Phosphine oxide 3d. A CIF file with the crystallographic data is available as Supporting Information File 2 and is also available on request from the Cambridge Crystallographic Data Centre as deposition 1046604. (congeners of vinyl sulfides) were found to react with Phosphine oxide 1a at 80 °C for about 30 and 20 h, respectively, to deliver difficult-to-separate mixtures of organophosphorus compounds ( 31 P NMR). Scheme 2: Addition of Secondary Phosphine sulfide to vinyl sulfide under aerobic catalyst-free conditions. To gain a primary insight into the reaction mechanism, several experiments were carried out. On example of Phosphine oxide 1a and vinyl sulfide 2c, we have shown that the reaction proceeds in the dark with the same efficiency as in the light. Therefore, the photochemical pathway of the reaction is hardly probable. Also, the reaction was established under an argon atmosphere. Under these conditions (argon, 80 °C for 18 h, exemplified by 1a/2c pair) the formation of products 3a-h does not take place and the starting Phosphine oxide remained almost intact ( 31 P NMR). This indicates that the reaction requires the presence of oxygen. In the other experiment, when TEMPO, a widely used radical scavenger, was added (10 mol %) into the reaction system 1a/2c, the product 3d was also formed, however, a longer reaction time was required for complete conversion of Secondary Phosphine oxide 1a as compared to TEMPO-free conditions (15 vs 11 h). Meanwhile, this observation does not completely exclude a radical mechanism since the cross-coupling reactions between TEMPO and radical intermediates can be reversible Taking these data into account, the following mechanism is suggested (Scheme 3). The first step is assumed to be the generation of phosphinoyl (A) and hydroperoxyl (HOO • ) radicals by the reaction of O 2 with Phosphine oxide 1. Earlier, the transfer of a hydrogen atom from the P(O)H species to molecular oxygen has been reported for example for Ph 2 P(O)H Although quantum chemical computations [MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p)] of the model radicals B and C (with R, R' = Me) reveals that the latter is energetically less preferred than the former, their energy difference is too small (4.38 kcal/mol) to completely prohibit the B→C transformation. Beilstein J. Org. Chem. 2015, 11, 1985-1990. 1989 Scheme 3: Putative mechanism. Conclusion In summary, we have disclosed an aerobic addition of Secondary Phosphine oxides to vinyl sulfides under solvent-and catalyst-free conditions, which provides an efficient approach to hitherto unknown 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)Phosphine oxides in one step. The synthesized Phosphine oxides, bearing hydroxy and sulfide functions, represent prospective building blocks for organic synthesis and interesting ligands for metal complexes. The results obtained contribute to the basic chemistry of both Phosphine oxides and vinyl sulfides
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catalyst free phosphorylation of acridine with Secondary Phosphine chalcogenides nucleophilic addition vs snhar reaction
Organic Letters, 2018Co-Authors: Pavel A Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, A I Albanov, B A TrofimovAbstract:Acridine adds Secondary Phosphine chalcogenides HP(X)R2 (X = O, S, Se; R = Ar, ArAlk) under catalyst-free conditions at 70–75 °C (both in the presence and absence of the electron-deficient acetylenes) to give 9-chalcogenophosphoryl-9,10-dihydroacridines in 61–94% yields. This contrasts with pyridines, which under similar conditions undergo an SNHAr reaction, wherein electron-deficient acetylenes play the role of oxidants. For acridine, the SNHAr step has been accomplished by the oxidation of the intermediate 9-phosphoryl-9,10-dihydroacridines (X = O) with chloranil.
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three component reaction of 4 methylpyridine with alkyl propiolates and Secondary Phosphine chalcogenides
Russian Journal of General Chemistry, 2018Co-Authors: Pavel A Volkov, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, N K Gusarova, A I Albanov, B A TrofimovAbstract:The reaction between 4-methylpyridine, alkyl propiolates, and Secondary Phosphine oxides proceeded as N-vinylation-C-phosphorylation with stereo- and regioselective formation of (E)-N-ethenyl-C2- phosphoryl-1,2-dihydropyridines [when using bis(2-phenylethyl)Phosphine oxide] or (E)-N-ethenyl-C4- phosphoryl-1,4-dihydropyridines (when using diphenylPhosphine oxide). The process occurred at 60–62°C within 3 h to give functional dihydropyridines in 40–82% yield. Under similar conditions, bis(2-phenylethyl) Phosphine sulfide and selenide reacted with alkyl propiolates preferably by nucleophilic PH-monoaddition at the triple bond.
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metal free site selective cross coupling of pyridines with Secondary Phosphine chalcogenides using acylacetylenes as oxidants
Chemical Communications, 2018Co-Authors: Boris A. Trofimov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, Pavel A Volkov, A I Albanov, O N ChupakhinAbstract: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.
B A Trofimov - One of the best experts on this subject based on the ideXlab platform.
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oxidative cross coupling of Secondary Phosphine chalcogenides with amino alcohols and aminophenols aspects of the reaction chemoselectivity
Organic and Biomolecular Chemistry, 2021Co-Authors: K. O. Khrapova, Nina K. Gusarova, L. I. Larina, A. A. Telezhkin, Pavel A Volkov, D V Pavlov, B A TrofimovAbstract:Secondary Phosphine chalcogenides react with primary amino alcohols under mild conditions (room temperature, molar ratio of the initial reagents 1 : 1) in a CCl4/Et3N oxidizing system to chemoselectively deliver amides of chalcogenophosphinic acids with free OH groups. Under similar conditions, mono-cross-coupling between Secondary Phosphine chalcogenides and 1,2- or 1,3-aminophenols proceeds only with the participation of phenolic hydroxyl to give aminophenylchalcogenophosphinic O-esters. The yields of the synthesized functional amides or esters are 60–85%.
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catalyst and solvent free hydrophosphorylation of ketones with Secondary Phosphine oxides green synthesis of tertiary α hydroxyPhosphine oxides
Synthesis, 2020Co-Authors: Nina K. Gusarova, L. I. Larina, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, Pavel A Volkov, D V Pavlov, Andrei V Afonin, B A TrofimovAbstract:Tertiary α-hydroxyPhosphine oxides have been synthesized via the catalyst- and solvent-free reaction between available Secondary Phosphine oxides and aliphatic, aromatic and heteroaromatic ketones at 20–62 °C in near to 96–98% yield. The developed method meets the requirements of green chemistry and the PASE (pot, atom, step economy) paradigm. According to quantum-chemical calculations at the B3LYP/6-311++G(d,p) level, the synthesized hydroxyPhosphine oxides feature a weak (≈3 kcal·mol–1) O−H···O=P intramolecular hydrogen bond.
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catalyst free regio and chemoselective addition of Secondary Phosphine oxides to isoquinolines
Russian Chemical Bulletin, 2020Co-Authors: Pavel A Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, A I Albanov, T I Vakulskaya, S S Khutsishvili, B A TrofimovAbstract:Isoquinolines react with Secondary Phosphine oxides without catalyst (70–75 °C, 10–15 h, without solvent or in MeCN) to chemo- and regioselectively form previously unknown diadducts, 1,3-bis(diorganylphosphoryl)-1,2,3,4-tetrahydroisoquinolines, in high yields (85–95%).
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catalyst free phosphorylation of acridine with Secondary Phosphine chalcogenides nucleophilic addition vs snhar reaction
Organic Letters, 2018Co-Authors: Pavel A Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, A I Albanov, B A TrofimovAbstract:Acridine adds Secondary Phosphine chalcogenides HP(X)R2 (X = O, S, Se; R = Ar, ArAlk) under catalyst-free conditions at 70–75 °C (both in the presence and absence of the electron-deficient acetylenes) to give 9-chalcogenophosphoryl-9,10-dihydroacridines in 61–94% yields. This contrasts with pyridines, which under similar conditions undergo an SNHAr reaction, wherein electron-deficient acetylenes play the role of oxidants. For acridine, the SNHAr step has been accomplished by the oxidation of the intermediate 9-phosphoryl-9,10-dihydroacridines (X = O) with chloranil.
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three component reaction of 4 methylpyridine with alkyl propiolates and Secondary Phosphine chalcogenides
Russian Journal of General Chemistry, 2018Co-Authors: Pavel A Volkov, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, N K Gusarova, A I Albanov, B A TrofimovAbstract:The reaction between 4-methylpyridine, alkyl propiolates, and Secondary Phosphine oxides proceeded as N-vinylation-C-phosphorylation with stereo- and regioselective formation of (E)-N-ethenyl-C2- phosphoryl-1,2-dihydropyridines [when using bis(2-phenylethyl)Phosphine oxide] or (E)-N-ethenyl-C4- phosphoryl-1,4-dihydropyridines (when using diphenylPhosphine oxide). The process occurred at 60–62°C within 3 h to give functional dihydropyridines in 40–82% yield. Under similar conditions, bis(2-phenylethyl) Phosphine sulfide and selenide reacted with alkyl propiolates preferably by nucleophilic PH-monoaddition at the triple bond.
Pavel A Volkov - One of the best experts on this subject based on the ideXlab platform.
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oxidative cross coupling of Secondary Phosphine chalcogenides with amino alcohols and aminophenols aspects of the reaction chemoselectivity
Organic and Biomolecular Chemistry, 2021Co-Authors: K. O. Khrapova, Nina K. Gusarova, L. I. Larina, A. A. Telezhkin, Pavel A Volkov, D V Pavlov, B A TrofimovAbstract:Secondary Phosphine chalcogenides react with primary amino alcohols under mild conditions (room temperature, molar ratio of the initial reagents 1 : 1) in a CCl4/Et3N oxidizing system to chemoselectively deliver amides of chalcogenophosphinic acids with free OH groups. Under similar conditions, mono-cross-coupling between Secondary Phosphine chalcogenides and 1,2- or 1,3-aminophenols proceeds only with the participation of phenolic hydroxyl to give aminophenylchalcogenophosphinic O-esters. The yields of the synthesized functional amides or esters are 60–85%.
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catalyst and solvent free hydrophosphorylation of ketones with Secondary Phosphine oxides green synthesis of tertiary α hydroxyPhosphine oxides
Synthesis, 2020Co-Authors: Nina K. Gusarova, L. I. Larina, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, Pavel A Volkov, D V Pavlov, Andrei V Afonin, B A TrofimovAbstract:Tertiary α-hydroxyPhosphine oxides have been synthesized via the catalyst- and solvent-free reaction between available Secondary Phosphine oxides and aliphatic, aromatic and heteroaromatic ketones at 20–62 °C in near to 96–98% yield. The developed method meets the requirements of green chemistry and the PASE (pot, atom, step economy) paradigm. According to quantum-chemical calculations at the B3LYP/6-311++G(d,p) level, the synthesized hydroxyPhosphine oxides feature a weak (≈3 kcal·mol–1) O−H···O=P intramolecular hydrogen bond.
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catalyst free regio and chemoselective addition of Secondary Phosphine oxides to isoquinolines
Russian Chemical Bulletin, 2020Co-Authors: Pavel A Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, A I Albanov, T I Vakulskaya, S S Khutsishvili, B A TrofimovAbstract:Isoquinolines react with Secondary Phosphine oxides without catalyst (70–75 °C, 10–15 h, without solvent or in MeCN) to chemo- and regioselectively form previously unknown diadducts, 1,3-bis(diorganylphosphoryl)-1,2,3,4-tetrahydroisoquinolines, in high yields (85–95%).
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catalyst free phosphorylation of acridine with Secondary Phosphine chalcogenides nucleophilic addition vs snhar reaction
Organic Letters, 2018Co-Authors: Pavel A Volkov, Nina K. Gusarova, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, A I Albanov, B A TrofimovAbstract:Acridine adds Secondary Phosphine chalcogenides HP(X)R2 (X = O, S, Se; R = Ar, ArAlk) under catalyst-free conditions at 70–75 °C (both in the presence and absence of the electron-deficient acetylenes) to give 9-chalcogenophosphoryl-9,10-dihydroacridines in 61–94% yields. This contrasts with pyridines, which under similar conditions undergo an SNHAr reaction, wherein electron-deficient acetylenes play the role of oxidants. For acridine, the SNHAr step has been accomplished by the oxidation of the intermediate 9-phosphoryl-9,10-dihydroacridines (X = O) with chloranil.
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three component reaction of 4 methylpyridine with alkyl propiolates and Secondary Phosphine chalcogenides
Russian Journal of General Chemistry, 2018Co-Authors: Pavel A Volkov, K. O. Khrapova, A. A. Telezhkin, N. I. Ivanova, N K Gusarova, A I Albanov, B A TrofimovAbstract:The reaction between 4-methylpyridine, alkyl propiolates, and Secondary Phosphine oxides proceeded as N-vinylation-C-phosphorylation with stereo- and regioselective formation of (E)-N-ethenyl-C2- phosphoryl-1,2-dihydropyridines [when using bis(2-phenylethyl)Phosphine oxide] or (E)-N-ethenyl-C4- phosphoryl-1,4-dihydropyridines (when using diphenylPhosphine oxide). The process occurred at 60–62°C within 3 h to give functional dihydropyridines in 40–82% yield. Under similar conditions, bis(2-phenylethyl) Phosphine sulfide and selenide reacted with alkyl propiolates preferably by nucleophilic PH-monoaddition at the triple bond.
