- Complexation and Versatile Reactivity of a Highly Lewis Acidic Cationic Mg Complex with Alkynes and Phosphines
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[(BDI)Mg+][B(C6F5)4?] (1; BDI=CH[C(CH3)NDipp]2; Dipp=2,6-diisopropylphenyl) was prepared by reaction of (BDI)MgnPr with [Ph3C+][B(C6F5)4?]. Addition of 3-hexyne gave [(BDI)Mg+?(EtC≡CEt)][B(C6F5)4?]. Single-crystal X-ray analysis, NMR investigations, Raman spectra, and DFT calculations indicate a significant Mg-alkyne interaction. Addition of the terminal alkynes PhC≡CH or Me3SiC≡CH led to alkyne deprotonation by the BDI ligand to give [(BDI-H)Mg+(C≡CPh)]2?2 [B(C6F5)4?] (2, 70 %) and [(BDI-H)Mg+(C≡CSiMe3)]2?2 [B(C6F5)4?] (3, 63 %). Addition of internal alkynes PhC≡CPh or PhC≡CMe led to [4+2] cycloadditions with the BDI ligand to give {Mg+C(Ph)=C(Ph)C[C(Me)=NDipp]2}2? 2 [B(C6F5)4?] (4, 53 %) and {Mg+C(Ph)=C(Me)C[C(Me)=NDipp]2}2?2 [B(C6F5)4?] (5, 73 %), in which the Mg center is N,N,C-chelated. The (BDI)Mg+ cation can be viewed as an intramolecular frustrated Lewis pair (FLP) with a Lewis acidic site (Mg) and a Lewis (or Br?nsted) basic site (BDI). Reaction of [(BDI)Mg+][B(C6F5)4?] (1) with a range of phosphines varying in bulk and donor strength generated [(BDI)Mg+?PPh3][B(C6F5)4?] (6), [(BDI)Mg+?PCy3][B(C6F5)4?] (7), and [(BDI)Mg+? PtBu3][B(C6F5)4?] (8). The bulkier phosphine PMes3 (Mes=mesityl) did not show any interaction. Combinations of [(BDI)Mg+][B(C6F5)4?] and phosphines did not result in addition to the triple bond in 3-hexyne, but during the screening process it was discovered that the cationic magnesium complex catalyzes the hydrophosphination of PhC≡CH with HPPh2, for which an FLP-type mechanism is tentatively proposed.
- Pahl, Jürgen,Stennett, Tom E.,Volland, Michel,Guldi, Dirk M.,Harder, Sjoerd
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Read Online
- Alkyl scandium complexes coordinated by dianionic O,N,N- and O,N,O-ligands derived from Schiff bases
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The reactions of imino phenols 3,5-But2-2-HOC6H2CH=NX (X = 8-C9H6N, 2-MeO-5-MeC6H3 and 2-PhOC6H4) with Sc(CH2SiMe3)3/
- Cherkasov, Anton V.,Gurina, Galina A.,Kissel, Alexander A.,Ob'edkov, Anatoly M.,Trifonov, Alexander A.
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p. 631 - 634
(2021/11/26)
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- A bench-stable copper photocatalyst for the rapid hydrophosphination of activated and unactivated alkenes
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Cu(acac)2 (1) is a highly active catalyst for the hydrophosphination of alkenes. Photocatalytic conditions are critical, and provide high conversions with unactivated substrates that have never before been reported with an air-stable catalyst or at ambient temperature. The commercial availability, ease of use, and broad substrate scope of compound 1 make hydrophosphination more available to synthetic chemists.
- Dannenberg, Steven G.,Waterman, Rory
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supporting information
p. 14219 - 14222
(2020/11/24)
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- N-Heterocyclic Carbene Non-Innocence in the Catalytic Hydrophosphination of Alkynes
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Studies on alkyne hydrophosphination employing nickel-NHC catalysts (NHC=N-heterocyclic carbene) revealed that the free N-alkyl substituted NHCs themselves were catalytically active. DFT calculations showed the mechanism involves the NHC acting as a Br?ns
- Blackaby, William J. M.,Neale, Samuel E.,Isaac, Connie J.,Sabater, Sara,Macgregor, Stuart A.,Whittlesey, Michael K.
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p. 1893 - 1897
(2019/04/14)
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- Photocatalytic Hydrophosphination of Alkenes and Alkynes Using Diphenylphosphine and Triamidoamine-Supported Zirconium
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Reactions of alkene or alkyne with diphenylphosphine and catalytic [κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr (1) are greatly enhanced under photolysis, providing viable catalytic hydrophosphination with a broad substrate scope. Whereas diphenylphosphine had been an inaccessible substrate under thermal conditions, complete conversion of alkene substrates to tertiary phosphine is achieved in as little as four hours at ambient temperature with 1 under ultraviolet irradiation. Previously inactive alkenes are now hydrophosphination substrates with diphenylphosphine to produce tertiary phosphine ligands possessing tunable steric and electronic properties.
- Novas, Bryan T.,Bange, Christine A.,Waterman, Rory
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supporting information
p. 1640 - 1643
(2019/01/04)
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- Thermally Stable Ln(II) and Ca(II) Bis(benzhydryl) Complexes: Excellent Precatalysts for Intermolecular Hydrophosphination of C-C Multiple Bonds
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A series of Ln(II) and Ca(II) bis(alkyl) complexes with bulky benzhydryl ligands, [(p-tBu-C6H4)2CH]2M(Ln) (M = Sm, L = DME, n = 2 (1); M = Sm, Yb, Ca, L = TMEDA, n = 1 (2, 3, 4), were synthesized by t
- Selikhov, Alexander N.,Plankin, Gleb S.,Cherkasov, Anton V.,Shavyrin, Andrey S.,Louyriac, Elisa,Maron, Laurent,Trifonov, Alexander A.
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p. 5325 - 5334
(2019/04/17)
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- Reductive Elimination at Carbon under Steric Control
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It has been previously demonstrated that stable singlet electrophilic carbenes can behave as metal surrogates in the activation of strong E-H bonds (E = H, B, N, Si, P), but it was believed that these activations only proceed through an irreversible activation barrier. Herein we show that, as is the case with transition metals, the steric environment can be used to promote reductive elimination at carbon centers.
- Tolentino, Daniel R.,Neale, Samuel E.,Isaac, Connie J.,MacGregor, Stuart A.,Whittlesey, Michael K.,Jazzar, Rodolphe,Bertrand, Guy
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supporting information
p. 9823 - 9826
(2019/07/04)
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- Calcium Amido Complexes Coordinated by Tridentate Amidinate Ligands: Synthesis, Structures and Catalytic Activity in Olefin Hydrophosphination and Polymerization of Cyclic Esters
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The reactions of [(Me3Si)2N]2Ca(thf)2 with amidines 2-(Ph2P=NPh)C6H4NHC(tBu)=N(2,6-R2C6H3) {R = iPr (L1H); R = Me (L2H)} af
- Tolpygin, Aleksei O.,Cherkasov, Anton V.,Fukin, Georgy K.,Kovylina, Tatyana A.,Lyssenko, Konstantin A.,Trifonov, Alexander A.
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p. 4289 - 4296
(2019/08/15)
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- Lithium-Aluminate-Catalyzed Hydrophosphination Applications
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Synthesized, isolated, and characterized by X-ray crystallography and NMR spectroscopic studies, lithium phosphidoaluminate iBu3AlPPh2Li(THF)3 has been tested as a catalyst for hydrophosphination of alkynes, alkenes, and carbodiimides. Based on the collective evidence of stoichiometric reactions, NMR monitoring studies, kinetic analysis, and DFT calculations, a mechanism involving deprotonation, alkyne insertion, and protonolysis is proposed for the [iBu3AlHLi]2 aluminate catalyzed hydrophosphination of alkynes with diphenylphosphine. This study enhances further the development of transition-metal-free, atom-economical homogeneous catalysis using common sustainable main-group metals.
- Pollard, Victoria A.,Young, Allan,McLellan, Ross,Kennedy, Alan R.,Tuttle, Tell,Mulvey, Robert E.
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supporting information
p. 12291 - 12296
(2019/08/02)
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- Regioselective Single and Double Hydrophosphination and Hydrophosphinylation of Unactivated Alkynes
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A lanthanum-based N,N-dimethylbenzylamine complex was used as a precatalyst for both hydrophosphination and hydrophosphinylation of alkynes under mild conditions. In the case of hydrophosphination, the catalyst induced monoaddition with high regiospecific
- Basiouny, Miriam M. I.,Dollard, Deborah A.,Schmidt, Joseph A. R.
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p. 7143 - 7153
(2019/08/26)
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- Mechanistic Investigation of Well-Defined Cobalt Catalyzed Formal E-Selective Hydrophosphination of Alkynes
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A formal E-selective hydrophosphination of terminal and internal alkynes catalyzed by a well-defined [Co(PMe3)4] (A) complex is achieved under mild conditions in good-to-excellent yield. The reaction does not require any additives and/or external base for an efficient hydrophosphination reaction. The reaction provided excellent scope and good functional tolerance. Detailed spectroscopic analysis (NMR, EPR, and UV-vis) revealed that the low valent cobalt(0) complex undergoes oxidative addition with diphenylphosphine, followed by hydrometalation with alkyne, and subsequent reductive elimination led to the expected product. The detailed spectroscopic analyses along with the isotopic labeled experiments facilitate to intercept the active intermediates that are involved in the catalytic cycle, which are detailed. It was revealed that the suprafacial (vide infra) delivery of H and phosphorus to π-alkynes in a syn-fashion led to formal E-vinyl phosphine.
- Rajpurohit, Jitendrasingh,Kumar, Pardeep,Shukla, Pragya,Shanmugam, Muralidharan,Shanmugam, Maheswaran
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p. 2297 - 2304
(2018/07/31)
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- Neutral and Cationic Zirconium Complexes Bearing Multidentate Aminophenolato Ligands for Hydrophosphination Reactions of Alkenes and Heterocumulenes
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Zirconium complexes supported by multidentate aminophenolato ligands were synthesized and characterized. The catalytic activities of neutral zirconium complexes and their cationic derivatives in the hydrophosphination of alkenes as well as heterocumulenes have been investigated and compared. Neutral complex 1 bearing a multidentate amino mono(phenolato) ligand exhibited high activity in hydrophosphination of simple alkenes, and anti-Markovnikov products were obtained in 37-94% yields at room temperature. Cationic species generated in situ from complex 3 stabilized by a bis(phenolato) ligand were found to be more active for hydrophosphination of heterocumulenes, i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67-93% yields. The Lewis acidity and coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.
- Zhang, Yu,Qu, Liye,Wang, Yaorong,Yuan, Dan,Yao, Yingming,Shen, Qi
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p. 139 - 149
(2018/01/11)
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- Sequential Addition of Phosphine to Alkynes for the Selective Synthesis of 1,2-Diphosphinoethanes under Catalysis. Well-Defined NHC-Copper Phosphides vs in Situ CuCl2/NHC Catalyst
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The well-defined NHC-copper phosphides [(NHC)CuPPh2]3 (1, NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr); 2, NHC = N,N-di-tert-butylimidazol-2-ylidene (ItBu)) have been prepared by the reaction of simple copper halides with HPPh2 in the presence of N-heterocyclic carbenes (NHCs). Complexes 1 and 2 enabled catalytic double hydrophosphination of alkyl and aryl terminal alkynes to yield 1,2-diphosphinoethanes selectively in good yields. On the basis of these results, the most efficient and pratical in situ CuCl2/NHC catalyst has been developed. It catalyzes the selective double hydrophosphination of the alkynes with high efficiency and a wide substrate scope and exhibits even better performance than the well-defined NHC-Cu phosphides. The mechanistic studies disclosed that the formation of a copper acetylide in the catalytic cycle played an important role in the acceleration of the catalytic process.
- Yuan, Jia,Zhu, Lizhao,Zhang, Jianying,Li, Jianfeng,Cui, Chunming
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p. 455 - 459
(2017/04/26)
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- Markovnikov versus anti-Markovnikov Hydrophosphination: Divergent Reactivity Using an Iron(II) β-Diketiminate Pre-Catalyst
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The ability to tune between different regioselectivities using a common pre-catalyst is an unusual yet highly desirable process. Here, we report the use of an iron(II) pre-catalyst that can be used to synthesize vinyl phosphines in a Markovnikov-selective
- King, Andrew K.,Gallagher, Kimberley J.,Mahon, Mary F.,Webster, Ruth L.
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supporting information
p. 9039 - 9043
(2017/07/11)
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- Synthesis of vinylphosphines and unsymmetric diphosphines: Iron-catalyzed selective hydrophosphination reaction of alkynes and vinylphosphines with secondary phosphines
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Iron complex-catalyzed regioselective single hydrophosphination of terminal arylalkynes with secondary phosphines was achieved. Unsymmetric 1,2-bis(phosphino)ethanes with different phosphino groups were obtained by using our catalytic systems. The structu
- Itazaki, Masumi,Katsube, Shinya,Kamitani, Masahiro,Nakazawa, Hiroshi
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supporting information
p. 3163 - 3166
(2016/02/20)
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- N-Heterocyclic Carbene-Ytterbium Amide as a Recyclable Homogeneous Precatalyst for Hydrophosphination of Alkenes and Alkynes
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The N-heterocyclic carbene-ytterbium(II) amides (NHC)2Yb[N(SiMe3)2]2 (1: NHC: 1,3,4,5-tetramethylimidazo-2-ylidene (IMe4); 2: NHC: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr)) and the NHC-stabilized rare-earth phosphide (IMe4)3Yb(PPh2)2 (3) have been synthesized and fully characterized. Complexes 1-3 are active precatalysts for the hydrophosphination of alkenes, alkynes, and dienes and exhibited much superior catalytic activity to that of the NHC-free amide (THF)2Yb[N(SiMe)2]2. Complex 1 is the most active precursor among the three complexes. In particular, complex 1 can be recycled and recovered from the reaction media after the catalytic reactions. Furthermore, it was found that complex 3 could catalyze the polymerization of styrene to yield atactic polystyrenes with low molecular weights. To the best of our knowledge, complex 1 represents the first rare-earth complex that can be recovered after catalytic reactions.
- Yuan, Jia,Hu, Hongfan,Cui, Chunming
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p. 5778 - 5785
(2016/04/20)
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- Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes
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The hydrophosphination of carbon-carbon multiple bonds has been generally performed under acid, base or metal catalysis in different solvents. Herein, alkyl and alkenyl tertiary phosphines are obtained by the addition of diphenylphosphine to alkenes and alkynes, respectively, in the absence of a solvent and a catalyst. In the presence of elemental sulfur, the corresponding alkyl and alkenyl tertiary phosphine sulfides are synthesized in a three-component process. These simple methods, which meet most of the principles of Green Chemistry, are highly regioselective towards the anti-Markovnikov products and diastereoselective towards the Z alkenyl phosphines. The mechanistic aspects of the reactions are also tackled and the efficiency of the latter is compared with that of the catalytic methods.
- Moglie, Yanina,González-Soria, María José,Martín-García, Iris,Radivoy, Gabriel,Alonso, Francisco
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p. 4896 - 4907
(2016/10/06)
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- Synthesis and molecular structures of divalent bridged bis(guanidinate) europium complexes and their application in intermolecular hydrophosphination of alkenes and alkynes
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The reaction of anhydrous EuCl3 with one equiv. of lithium salt of a three-carbon bridged bis(guanidinate) Li2L1 (L1 = [iPr(Me3Si)NC(NiPr)N(CH2)3NC(NiPr)N(SiMe3)iPr]) in THF afforded chloride EuIIIL1Cl(THF)2 (1). The reduction reaction of complex 1 with Na/K alloy in a molar ratio of 1?:?1.2 in THF gave a novel EuII complex supported by an unexpected new bridged bis(guanidinate) ligand L3, [EuIIL3]2 (L3 = [iPr(Me3Si)NC(NiPr)N(CH2)3N(SiMe3)C(NiPr)2]) (2), through the redistribution of one guanidinate in L1 during the reduction. Complex 2 was structurally characterized to be a binuclear complex in which two Eu metals are connected together by two L3 ligands that adopted a μ-η1:η2:η2 coordination mode for one L3 ligand and a μ-η2:η2:η2 mode for the other. Treatment of the in situ formed EuIIIL2Cl(THF)2 (L2 = 1,8-C10H6{NC(NiPr)(NHiPr)}2) by the reaction of EuCl3 with 0.5 equiv. of [Li2L22Li2] in THF with Na/K alloy yielded a novel EuII complex [EuIIL2(THF)]2 (3) in good yield. Complex 3 was characterized by an X-ray crystal structure analysis. Complex 3 features an unusual μ-η1:η2:η2 coordination mode of the bridged bis(guanidinate) ligand onto EuII. Complexes 2 and 3 are efficient pre-catalysts for the intermolecular hydrophosphination of alkenes and alkynes to give exclusively anti-Markovnikov products and mainly anti-addition products for the alkyne reactions. For these transformations, the best performances were observed with complex 2.
- Liu, Qianqian,Wang, Chuanyong,Zhang, Xingmin,Xue, Mingqiang,Yao, Yingming,Zhang, Yong,Shen, Qi
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supporting information
p. 10447 - 10454
(2016/12/06)
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- Double hydrophosphination of alkynes promoted by rhodium: The key role of an N-heterocyclic carbene ligand
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The regioselective double hydrophosphination of alkynes mediated by rhodium catalysts is presented. The distinctive stereoelectronic properties of the NHC ligand prevent the catalyst deactivation by diphosphine coordination thereby allowing for the closing of a productive catalytic cycle.
- Di Giuseppe, Andrea,De Luca, Roberto,Castarlenas, Ricardo,Pérez-Torrente, Jesús J.,Crucianelli, Marcello,Oro, Luis A.
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supporting information
p. 5554 - 5557
(2016/05/09)
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- Synthesis of calcium and ytterbium complexes supported by a tridentate imino-amidinate ligand and their application in the intermolecular hydrophosphination of alkenes and alkynes
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Well-defined calcium and ytterbium complexes [{2-NC(Ph)NArC 6H4CHNAr}M{N(SiMe3)2}(THF)] (M = Ca, Yb; Ar = 2,6-iPr2C6H3) have been synthesized and characterized. They catalyze the
- Hu, Hongfan,Cui, Chunming
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experimental part
p. 1208 - 1211
(2012/04/10)
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- Regioselective double hydrophosphination of terminal arylacetylenes catalyzed by an iron complex
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The first catalytic double hydrophosphination of alkynes was achieved by reaction with diarylphosphines in the presence of an iron catalyst. The double hydrophosphination proceeded regioselectively and effectively for various secondary arylphosphines and
- Kamitani, Masahiro,Itazaki, Masumi,Tamiya, Chihiro,Nakazawa, Hiroshi
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supporting information; experimental part
p. 11932 - 11935
(2012/09/08)
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- Insertion reactions and catalytic hydrophosphination by triamidoamine-supported zirconium complexes
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Triamidoamine-supported zirconium phosphido complexes, (N 3N)ZrPRR′ (N3N = N(CH2CH 2NSiMe3)33-; R = alkyl, aryl; R′ = R, H), have been shown to catalyze the hydrophosphination of
- Roering, Andrew J.,Leshinski, Sarah E.,Chan, Stephanie M.,Shalumova, Tamila,MacMillan, Samantha N.,Tanski, Joseph M.,Waterman, Rory
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experimental part
p. 2557 - 2565
(2010/08/05)
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- Alkenylzirconocene-mediated preparation of alkenylphosphines
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(Chemical Equation Presented) Alkenylphosphines with various substituents were prepared by the reaction of an alkenylzirconocene with a chlorophosphine. Reactions of (α-unsubstituted alkenyl)zirconocenes with Ph2PCl or PhPCl2 gave th
- Miyaji, Taichi,Xi, Zhenfeng,Ogasawara, Masamichi,Nakajima, Kiyohiko,Takahashi, Tamotsu
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p. 8737 - 8740
(2008/03/13)
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- Regio- and stereoselective synthesis of alkenylphosphines: A rhodium-catalyzed hydrophosphination of alkynes using a silylphosphine
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(Chemical Equation Presented) A novel rhodium-catalyzed hydrophosphination of alkynes using a silylphosphine as a phosphino group source is described. A variety of alkynes, both terminal and internal ones with aryl, alkyl, and carboxyl groups, gave the co
- Hayashi, Minoru,Matsuura, Yutaka,Watanabe, Yutaka
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p. 9248 - 9251
(2007/10/03)
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- Cobalt-catalyzed syn hydrophosphination of alkynes
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Treatment of terminal and internal alkynes with diphenylphosphane in the presence of catalytic amounts of a base and cobalt (II) acetylacetonate affords, with perfect and universal syn selectivity, the (E)-alkenyldiphenylphosphane derivatives in good yiel
- Ohmiya, Hirohisa,Yorimitsu, Hideki,Oshima, Koichiro
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p. 2368 - 2370
(2007/10/03)
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- Nickel-catalyzed cross-coupling of diphenylphosphine with vinyl bromides and chlorides as a route to diphenylvinylphosphines
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An efficient nickel-catalyzed reaction for the phosphination of vinyl bromides and chlorides was developed. The procedure uses a combination of up to 1 mol% of nickel acetylacetonate, triethylamine and dimethylformamide as a solvent. The double bond geometry of the vinyl halides was retained under the reaction conditions.
- Shulyupin, Mstilsav O.,Chirkov, Evgeniy A.,Kazankova, Marina A.,Beletskaya, Irina P.
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p. 658 - 660
(2007/10/03)
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- Fluoride-mediated phosphination of alkenes and alkynes by silylphosphines
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Regioselective phosphination of carbon-carbon unsaturated bonds by a fluoride-mediated reaction of silylphosphines is described. Alkenes and alkynes having a directing group, such as an aromatic or a carbonyl group, reacted to form a carbon-phosphorus bon
- Hayashi, Minoru,Matsuura, Yutaka,Watanabe, Yutaka
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p. 9167 - 9169
(2007/10/03)
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- Intermolecular hydrophosphination of alkynes and related carbon-carbon multiple bonds catalyzed by organoytterbiums
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Intermolecular hydrophosphination of alkynes with diphenylphosphine is catalyzed by a Yb - imine complex, [Yb(η2-Ph 2CNPh)(hmpa)3], to give alkenylphosphines and phosphine oxides after oxidative workup in good yields under
- Takaki, Ken,Koshoji, Go,Komeyama, Kimihiro,Takeda, Mitsuhiro,Shishido, Tetsuya,Kitani, Akira,Takehira, Katsuomi
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p. 6554 - 6565
(2007/10/03)
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- Synthesis of vinylphosphines by hydrophosphination of alkynes in the presence of transition metal complexes
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Intermolecular hydrophosphination of terminal and internal alkynes with diphenylphosphine, catalyzed by palladium and nickel complexes, was accomplished for the first time. The reaction follows the syn-addition pattern. Conditions were found which ensure
- Kazankova,Efimova,Kochetkov,Afanas'ev,Beletskaya
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p. 1465 - 1474
(2007/10/03)
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- Reactivity of lithium diphenylphosphonium diylides towards phosphorus electrophiles: Synthesis of α,β-unsaturated phosphorus compounds
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The study of the reactivity of non-stabilized, semi-stabilized and stabilized lithium diphenylphosphonium diylides 1-4 towards Ph2PCl, allowed the synthesis of various α,β-unsaturated phosphines 13-14, via the intermediate formation of the corresponding functionalized monoylides 9-10 and their in situ reaction with carbonyl compounds. In many cases, the reaction is Z-stereoselective and the created double bond can be di- or also trisubstituted. The precise 1H-NMR study of the phosphines 13a-d and the X-ray analysis of 13a (Z isomer) allowed us to assign without ambiguity the stereochemistry of these compounds and to solve a 1H-NMR question. Contrary to reported results in the literature for 13a, we have shown that for the double bond of this phosphine, there is no exception to the general rule 3JHH(trans) > 3JHH(cis). The extension of this reactivity study to other phosphorus electrophiles such as Ph2P(O)Cl, Ph2P(S)Cl and (EtO)2P(O)Cl allowed, as preliminary results, the E-stereoselective synthesis of styrylphosphine oxide and sulfide and diethyl styrylphosphonate.
- Taillefer, Marc,Cristau, Henri Jean,Fruchier, Alain,Vicente, Virginie
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p. 307 - 315
(2007/10/03)
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- New approach to vinylphosphines based on Pd- and Ni-catalyzed diphenylphosphine addition to alkynes
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The catalytic addition of Ph2PH to phenylacetylene regioselectively leads to the Ph2P-CH=CHPh isomer with Pd(PPh3)4 in acetonitrile and to the Ph2P-C(Ph)=CH2 isomer with Ni(acac)2/(EtO)2P(O)H in benzene. High selectivity were also obtained for the catalytic addition of Ph2PH to tBuC≡CH and to PhC≡CPh.
- Kazankova,Efimova,Kochetkov,Afanas'ev,Beletskaya,Dixneuf
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p. 497 - 500
(2007/10/03)
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- Synthesis of Vinyldiphenylphosphines by Pd-Catalyzed Cross-Coupling Reaction of Diphenylphosphine with Alkenylhalides
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α- and β-alkoxy (α- and β-dialkylamino)vinylphosphines were synthesized by palladium catalyzed reactions of the corresponding vinylhalides with diphenylphosphine or diphenyltrimethylsilylphosphine in high yields.
- Kazankova, Marina A.,Chirkov, Evgeniy A.,Kochetkow, Andrew N.,Efimova, Irina V.,Beletskaya, Irina P.
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p. 572 - 576
(2007/10/03)
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- Stereo-controlled synthesis of styrylphosphines and their oxides or sulfides using phosphonium diylides
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Lithium dimethyldiphenylphosphonium diylide reacts with electrophiles such as Ph2PCl, Ph2P(O)Cl or Ph2P(S)Cl to give monoylide intermediates allowing by reaction with benzaldehyde the synthesis of the styrylphosphines or the corresponding oxides or sulfides. This efficient one-pot method permits at choice the selective synthesis of each isomer Z or E and corroborates further the isomeric identification of the styrylphosphines.
- Taillefer,Cristau
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p. 7857 - 7860
(2007/10/03)
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- ACETYLENIC HYDROCARBONS AND VINYL HALIDES IN THE ALKYLATION OF PH ACIDS UNDER CONDITIONS OF PHASE-TRANSFER CATALYSIS OR IN SUPERBASIC MEDIUM
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By the reaction of nonactivated acetylenes with diphenylphosphine under phase-transfer catalysis or in superbasic medium the corresponding mono- and diphosphines were obtained, whereas with diphenylphosphine oxide only bis(phosphine oxides) were formed.Diphenylphosphine was found to react with 1,1- and 1,2-dichloroethenes, as well as with 1,1,2-trichloroethane, yielding 1,2-bis(diphenylphosphino)ethene.The reactions of E-1-chloro-2-phenyl- and 1-chloro-1-phenylethenes with diphenylphosphine under similar conditions lead either to E-1-diphenylphosphino-2-phenylethene or to bisphosphine with a ratio of reactants of 1:1 or 1:2 respectively.Diphenylphosphine oxide gives bis(phosphine oxides) in all the above cases.Stereochemistry and mechanism of the reactions are discussed.
- Khachatryan, R. A.,Grigoryan, N. Yu.,Indzhikyan, M. G.
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p. 1134 - 1138
(2007/10/02)
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- CROSS COUPLING OF SISLYLPHOSPHINES WITH SUBSTITUTED VINYL HALIDES AS A METHOD FOR THE SYNTHESIS OF 2-ALKENYLPHOSPHINES
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The complexes of zerovalent palladium catalyze the cross coupling of alkenyl bromides with the monosilylated derivatives of secondary and primary phosphines.The yields of the obtained tertiary phosphines amount to 70-85percent while the yields of the secondary phosphines are somewhat lower, and this is explained by side processes.The effect of the steric characteristics of the substituents in the reagents on the ease of cross coupling was examined.
- Veits, Yu. A.,Karlstedt, N. B.,Beletskaya, I. P.
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- Preparation of vinylphosphines by means of free radical addition of diphenylphosphine to alkynes and allenes
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Diphenylphosphine adds readily to alkynes and allenes under free radical conditions.Alkynes normally give E-vinylphosphines as the primary (kinetic) product, but Z-vinylphosphines are the main products isolated.Allenes generally give complex product mixtures in which the predominant components are vinyl phosphines formed via addition of the Ph2P. radical to the central carbon atom of the allene fragment.
- Mitchell, Terence N.,Heesche, Kerstin
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p. 163 - 170
(2007/10/02)
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- Preparation of β-Substituted trans-Ethylene Diphenylphosphines and Sulphides by P(O) and P(S)-activated Olefination
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Methylene bis-diphenylphosphine monoxide (3c) in toluene reacts regiospecifically and stereoselectively with aldehydes in the presence of potassium tert-butoxide to β-substituted trans-ethylene diphenylphosphines 6, which can be oxidized to the sulphides 2 by sulphur in acetone.These sulphides 2 are to be obtained also directly from methylene bis-diphenylphosphine oxide sulphide 3b and methylene bis-diphenylphosphine disulphide 3d, respectively, under the same olefination conditions.But the yields are smaller and the purification of the raw products is much more difficult, if 3d is used.
- Gloyna, Dieter
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p. 360 - 366
(2007/10/02)
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- The 1H, 13C and 31P NMR Spectra of EZ Pairs of some Phosphorus Substituted Alkenes
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The olefins Ph2P(X)CH=CHR have been prepared and their 1H, 13C and 31P NMR spectra measured. trans 3J (range 18.3-25.7 Hz> is greater than cis 3J (range 6.9-11 Hz) but thi
- Duncan, Mark,Gallagher, Michael J.
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- Compound oxidized styrylphosphine
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Homopolymers, copolymers and terpolymers of a styrene based monomer are prepared by: (1) polymerizing at least one oxidized styrylphosphine monomer selected from the group of: (2) polymerizing p-diphenylphosphinestyrene and then oxidizing said polymerized p-diphenylphosphinestyrene monomer with an organoazide selected from the group of (C6 H5)2 P(O)N3, (C6 H5 O)2 P(O)N3, (C6 H5)2 C3 N3 (N3) and C6 H5 C3 N3 (N3)2. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer selected from the group of:
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- P-Styryldiethylphosphine
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Hydroformylation reactions are carried out in the presence of a catalyst comprising a solid polymer of a trivalent phosphorus-containing compound having associated therewith a metal of the group cobalt, rhodium, ruthenium, platinum and palladium. The poly
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