- Copper-Catalyzed Vicinal Cyano-, Thiocyano-, and Chlorophosphorylation of Alkynes: A Phosphinoyl Radical-Initiated Approach for Difunctionalized Alkenes
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A copper-catalyzed difunctional cyano-, thiocyano-, and chlorophosphorylation reaction of alkynes with P(O)-H compounds and coupling partners (TBACN, TMSNCS, TMSCl) is described. The reaction introduces versatile groups (-P(O)R2 and -CN, -SCN, or -Cl) to form tri- and tetrasubstituted alkenyl phosphine oxides/phosphonates regio- and stereoselectively.
- Li, Cheng-Kun,Li, Jian-An,Shoberu, Adedamola,Tao, Ze-Kun,Zhang, Wei,Zou, Jian-Ping
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supporting information
p. 4342 - 4347
(2021/06/28)
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- Oxidative Addition of Secondary Phosphine Oxides through Rh(I) Center: Hydrido-Phosphinito-Rh(III) Complexes and their Catalytic Activity in Hydrophosphinylation of Alkynes
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The reaction of [Rh(μ-Cl)(cod)]2 with diimines, differing in their steric and electronic properties, and with diphenylphosphine oxide leads to the oxidative addition products, hydrido-phosphinito-Rh(III) complexes {Rh(PPh2OH)(PPh2O)(NN)(H)Cl} (1), stabilized by the formation of a hydrogen bonded phosphinous acid-phosphinito quasi-chelate [(PO???HOP)-κ2P]. Exchange of hydride by chloride to afford {Rh(PPh2OH)(PPh2O)(NN)Cl2} (2) occurs in hydrido complexes containing low steric hindrance diimines and is inhibited for complexes containing encumbered diimines. Complexes 1 react with BF3?OEt2 with exchange of the acidic proton by BF2, and transformation of the quasi-chelating PO???HOP into a chelating PO-BF2-OP ligand in {Rh{(PPh2O)2BF2}(NN)(H)Cl} (3). The reaction of [Rh(μ-Cl)(nbd)]2 or [Rh(acac)(nbd)] with diphenylphosphine oxide leads to coordinatively unsaturated nortricyclyl-phosphinito-Rh(III) complexes, {Rh(PPh2OH)(PPh2O)(ntyl)(μ-Cl)}2 (4) or {Rh(PPh2OH)(PPh2O)(ntyl)(acac)} (6), respectively. Their reaction with BF3?OEt2 results in the corresponding {Rh{(PPh2O)2BF2}(ntyl)(μ-Cl)}2 (5) or {Rh{(PPh2O)2BF2}(ntyl)(acac)} (7). Some of these new complexes have shown catalytic activity in hydrophosphinylation of alkynes, with {Rh(PPh2OH)(PPh2O)(NN)(H)Cl} containing encumbered NN being efficient and regioselective catalysts in the hydrophosphinylation of phenylacetylene with diphenylphosphine oxide to produce (E)-diphenyl(styryl)phosphine oxide.
- Almenara, Naroa,Barquin, Montserrat,Huertos, Miguel A.,Garralda, María A.
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supporting information
p. 4935 - 4945
(2021/11/09)
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- Knoevenagel Condensation of Phosphinoylacetic Acids with Aldehydes: An Efficient One-Pot Strategy for the Synthesis of P-Functionalized Alkenyl Compounds
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A wide range of commercially available aldehydes have been applied to Knoevenagel condensation reaction to give E -alkenylphosphine oxides and vinylphosphine oxides. The readily available phosphinoylacetic acids derived from P(O)-H compounds were used as the starting materials in the reaction, providing a highly stereoselective and efficient method for constructing α,β-unsaturated phosphine oxides. Moreover, this simple and practical procedure provides an alternative and more environmentally friendly synthesis strategy for this type of P-functionalized alkenyl compounds.
- Dziuba, Kamil,Frynas, S?awomir,Szwaczko, Katarzyna
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p. 2142 - 2154
(2021/01/21)
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- Heterogeneous Catalytic Method for the Copper(II)-Catalysed Addition of H-Phosphinates and Secondary Phosphine Oxides to Phenylacetylene
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Copper(II) on 4?? molecular sieve was found to be an efficient heterogeneous catalyst in the addition of different H-phosphinates and secondary phosphine oxides to phenylacetylene. All hydrophosphinylation reactions were completely regioselective, as only β-isomers were formed, and the E-alkenylphosphinates and E-alkenylphosphine oxides were synthesized in moderate to excellent yields. The catalyst could be reused multiple times in the reaction. Graphic Abstract: [Figure not available: see fulltext.]
- Bagi, Péter,Hell, Zoltán,Juhász, Kinga,Varga, Bence
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- Nickel-catalyzed coupling of R2P(O)Me (R = aryl or alkoxy) with (hetero)arylmethyl alcohols
-
α-Alkylation of methyldiarylphosphine oxides with (hetero)arylmethyl alcohols was performed under nickel catalysis. Various arylmethyl and heteroarylmethyl alcohols can be used in this transformation. A series of methyldiarylphosphine oxides were alkylated with 30-90% yields. Functional groups on the aromatic rings of methyldiarylphosphine oxides or arylmethyl alcohols including OMe, NMe2, SMe, CF3, Cl, and F groups can be tolerated. The conditions are also suitable for the α-alkylation reaction of dialkyl methylphosphonates.
- Li, Wei-Ze,Wang, Zhong-Xia
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p. 2233 - 2242
(2021/03/24)
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- Scope and Limitations of the s-Block Metal-Mediated Pudovik Reaction
-
The hydrophosphorylation of phenylacetylene with di(aryl)phosphane oxides Ar2P(O)H (Pudovik reaction) yields E/Z-isomer mixtures of phenylethenyl-di(aryl)phosphane oxides (1). Alkali and alkaline-earth metal di(aryl)phosphinites have been studi
- Fener, Benjamin E.,Schüler, Philipp,Ueberschaar, Nico,Bellstedt, Peter,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
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supporting information
p. 7235 - 7243
(2020/05/18)
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- Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds
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The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.
- Xu, Kaiqiang,Liu, Long,Li, Zhaohui,Huang, Tianzeng,Xiang, Kang,Chen, Tieqiao
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p. 14653 - 14663
(2020/12/29)
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- Cobaloxime Catalysis: selective synthesis of alkenylphosphine oxides under visible light
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Direct activation of H-phosphine oxide to react with an unsaturated carbon-carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in both synthetic and material fields. However, expensive metals and strong oxidants are typically required to realize the transformation. Here, we demonstrate the utility of earth-abundant cobaloxime to convert H-phosphine oxide into its reactive radical species under visible light irradiation. The radical species thus generated can be utilized to functionalize alkenes and alkynes without any external photosensitizer and oxidant. The coupling with terminal alkene generates E-alkenylphosphine oxide with excellent chemo- A nd stereoselectivity. The reaction with terminal alkyne yields linear E-alkenylphosphine oxide via neutral radical addition, while addition with internal ones generates cyclic benzophosphine oxides and hydrogen. Mechanistic studies on radical trapping experiments, electron spin resonance studies, and spectroscopic measurements confirm the formation of phosphinoyl radical and cobalt intermediates that are from capturing the electron and proton eliminated from H-phosphine oxide. The highlight of our mechanistic investigation is the dual role played by cobaloxime, viz., both as the visible light absorber to activate the P(O)-H bond as well as a hydrogen transfer agent to influence the reaction pathway. This synergetic feature of the cobaloxime catalyst preforming multiple functions under ambient condition provides a convergent synthetic approach to vinylphosphine oxides directly from H-phosphine oxides and alkenes (or alkynes).
- Liu, Wen-Qiang,Lei, Tao,Zhou, Shuai,Yang, Xiu-Long,Li, Jian,Chen, Bin,Sivaguru, Jayaraman,Tung, Chen-Ho,Wu, Li-Zhu
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p. 13941 - 13947
(2019/09/30)
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- Cobaloxime Catalysis: Selective Synthesis of Alkenylphosphine Oxides under Visible Light
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Direct activation of H-phosphine oxide to react with an unsaturated carbon-carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in both synthetic and material fields. However, expensive metals and strong oxidants are typically required to realize the transformation. Here, we demonstrate the utility of earth-abundant cobaloxime to convert H-phosphine oxide into its reactive radical species under visible light irradiation. The radical species thus generated can be utilized to functionalize alkenes and alkynes without any external photosensitizer and oxidant. The coupling with terminal alkene generates E-alkenylphosphine oxide with excellent chemo- and stereoselectivity. The reaction with terminal alkyne yields linear E-alkenylphosphine oxide via neutral radical addition, while addition with internal ones generates cyclic benzophosphine oxides and hydrogen. Mechanistic studies on radical trapping experiments, electron spin resonance studies, and spectroscopic measurements confirm the formation of phosphinoyl radical and cobalt intermediates that are from capturing the electron and proton eliminated from H-phosphine oxide. The highlight of our mechanistic investigation is the dual role played by cobaloxime, viz., both as the visible light absorber to activate the P(O)-H bond as well as a hydrogen transfer agent to influence the reaction pathway. This synergetic feature of the cobaloxime catalyst preforming multiple functions under ambient condition provides a convergent synthetic approach to vinylphosphine oxides directly from H-phosphine oxides and alkenes (or alkynes).
- Liu, Wen-Qiang,Lei, Tao,Zhou, Shuai,Yang, Xiu-Long,Li, Jian,Chen, Bin,Sivaguru, Jayaraman,Tung, Chen-Ho,Wu, Li-Zhu
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p. 13941 - 13947
(2019/09/30)
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- Practical C–P bond formation via heterogeneous photoredox and nickel synergetic catalysis
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An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis. This platform utilizing cadmium sulfide semiconductors as heterogeneous photocatalysts and
- Koranteng, Ernest,Liu, Yi-Yin,Liu, Si-Yue,Wu, Qiang-Xian,Lu, Liang-Qiu,Xiao, Wen-Jing
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p. 1841 - 1846
(2019/11/11)
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- Cycloaddition of Vinylphosphine Oxides to α-Oxy- o-xylylene as a route to Phosphorylated Naphthyl and Biaryl Scaffolds
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α-Oxy-o-xylylene, a highly reactive diene readily accessible from benzocyclobutenol, undergoes Diels-Alder reaction with vinylphosphine oxides, yielding the corresponding 2-phosphorylated 1-hydroxy-1,2,3,4-tetrahydronaphthalenes in excellent yields. Use of unsubstituted and trans-2-aryl-substituted vinylphosphine oxides leads to cycloadducts with complete regioselectivity and with cis/trans selectivity up to 19:1 in the most favorable case. In the case of P-stereogenic trans-2-aryl-substituted vinylphosphine oxides, a virtually complete chirality transfer from P to C can be achieved. Dehydration and aromatization of the obtained cycloadducts bearing the resolved P-stereogenic phosphinoyl groups can be carried out to afford the valuable P-stereogenic and axially chiral phosphorylated 1,2′-binaphthyl ring system. Cases of restricted rotation around Csp3-Csp2 single bond in some tetrahydronaphthalene cycloadducts have also been revealed.
- Frynas, S?awomir,?astawiecka, El?bieta,Kozio?, Anna E.,Flis, Anna,Pietrusiewicz, K. Micha?
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p. 1818 - 1832
(2019/02/05)
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- Ceric(IV) Ammonium Nitrate Mediated Phosphorylation of Alkenes: Easy Access to (E)-Vinylphosphonates
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An inexpensive Ceric(IV) ammonium nitrate mediated phosphorylation of alkenes has been developed. Without adding expensive metals and other additives, various (E)-alkenylphosphane oxides are obtained through an easy route in a one-pot manner. Preliminary
- Shen, Jian,Yu, Rui-Xiao,Luo, Yan,Zhu, Li-Xuan,Zhang, Yue,Wang, Xue,Xiao, Bo,Cheng, Jian-Bo,Yang, Bin,Li, Gui-Zhi
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supporting information
p. 2065 - 2070
(2019/03/07)
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- Cerium(IV)-Promoted Phosphinoylation-Nitratation of Alkenes
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A Cerium(IV)-promoted phosphinoylation-nitratation of alkenes is established under mild conditions. In this process, Ceric ammonium nitrate (CAN) acts as a cheap phosphorus-radical initiator, as well as a nitrate donor. Various β-nitrooxyphosphonates are
- Yang, Bin,Hou, Shu-Min,Ding, Shi-Yu,Zhao, Xiao-Nan,Gao, Yuan,Wang, Xue,Yang, Shang-Dong
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supporting information
p. 4470 - 4474
(2018/10/20)
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- Preparation method of alkenyl diphenylphosphine compound
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The invention discloses a preparation method of an alkenyl diphenylphosphine compound. The method adopts a derivative of aryl ethylene and diphenylphosphine oxide as initial raw materials, under the protection of nitrogen, ceric ammonium nitrate is also added, a molar ratio of the derivative of aryl ethylene to diphenylphosphine oxide to ceric ammonium nitrate is (2 to 3): 1: (1 to 3), the concentration of the solution is 0.2 mol/L (relative to the diphenylphosphine oxide) by adding an organic solvent, then the mixed solution reacts for 6 hours at the reaction temperature of 40 DEG C, then thetemperature increases to 90 DEG C to react for 12 hours until the reaction is ended, the solvent is removed in a rotary evaporation manner, and the alkenyl diphenylphosphine compound is obtained by virtue of column chromatography. The method of the invention is simple in reaction system, easy in obtaining the initial raw materials, convenient in operation, and wider in substrate applicability.
- -
-
Paragraph 0024; 0225; 0026; 0027; 0031; 0032
(2018/11/03)
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- Transition-metal-free C-P bond formation via decarboxylative phosphorylation of cinnamic acids with P(O)H compounds
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A novel, transition-metal-free phosphorylation of cinnamic acids with P(O)H compounds has been developed via radical-promoted decarboxylation under mild conditions. This method provides simple, efficient, and versatile access to valuable (E)-alkenylphosphine oxides in satisfactory yields with a wide variety of substrates.
- Liu, Lixin,Zhou, Dan,Dong, Jianyu,Zhou, Yongbo,Yin, Shuang-Feng,Han, Li-Biao
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p. 4190 - 4196
(2018/04/14)
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- Hydrophosphorylation of Alkynes Catalyzed by Palladium: Generality and Mechanism
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We carried out a comprehensive study on the generality, scope, limitations, and mechanism of the palladium-catalyzed hydrophosphorylation of alkynes with P(O)-H compounds (i.e., H-phosphonates, H-phosphinates, secondary phosphine oxides, and hypophosphinic acid). For H-phosphonates, Pd/dppp was the best catalyst. Both aromatic and aliphatic alkynes, with a variety of functional groups, were applicable to produce the Markovnikov adducts in high yields with high regioselectivity. Aromatic alkynes showed higher reactivity than aliphatic alkynes. Terminal alkynes reacted faster than internal alkynes. Sterically crowded H-phosphonates disfavored the addition. For H-phosphinates and secondary phosphine oxides, Pd/dppe/Ph2P(O)OH was the catalyst of choice, which led to highly regioselective formation of the Markovnikov adducts. By using Pd(PPh3)4 as the catalyst, hypophosphinic acid added to terminal alkynes to give the corresponding Markovnikov adducts. Phosphinic acids, phosphonic acid, and its monoester were not applicable to this palladium-catalyzed hydrophosphorylation. Mechanistic studies showed that, with a terminal alkyne, (RO)2P(O)H reacted, like a Br?nsted acid, to selectively generate the α-alkenylpalladium intermediate via hydropalladation. On the other hand, Ph(RO)P(O)H and Ph2P(O)H gave a mixture of α- and β-alkenylpalladium complexes. In the presence of Ph2P(O)OH, hydropalladation with this acid took place first to selectively generate the α-alkenylpalladium intermediate. A subsequent ligand exchange with a P(O)H compound gave the phosphorylpalladium intermediate which produced the Markovnikov adduct via reductive elimination. Related intermediates in the catalytic cycle were isolated and characterized.
- Chen, Tieqiao,Zhao, Chang-Qiu,Han, Li-Biao
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supporting information
p. 3139 - 3155
(2018/03/08)
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- Direct synthesis of alkynylphosphonates from alkynes and phosphite esters catalyzed by Cu/Cu2O nanoparticles supported on Nb2O5
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The aerobic oxidative coupling of alkynes and phosphite esters can be catalyzed by Cu/Cu2O nanoparticles supported on Nb2O5 (Cu/Cu2O@Nb2O5) to efficiently afford alkynylphosphonates. The catalyst can be reused by filtration and reduction. According to the results of control experiments and characterization data, the supporter Nb2O5 can reduce the electronic density of Cu and absorb the phosphite esters due to its strong Lewis acid sites, which may enhance the reaction efficiently.
- Yuan, Tao,Chen, Fei,Lu, Guo-ping
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p. 13957 - 13962
(2018/08/21)
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- Cu(i)/Fe(III)-Catalyzed C-P cross-coupling of styrenes with H-phosphine oxides: A facile and selective synthesis of alkenylphosphine oxides and β-ketophosphonates
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Cu(i)/Fe(iii)-Catalyzed phosphorylation and oxyphosphorylation of styrenes with H-phosphonates which can be controlled by varying the reaction temperature are developed. This study offers a new and expedient strategy for the synthesis of useful alkenylphosphine oxides and β-ketophosphonates in satisfactory yields. Moreover, the transformation is proposed to proceed via a radical process and exhibits a broad substrate scope and good functional group tolerance.
- Gu, Jian,Cai, Chun
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supporting information
p. 4226 - 4230
(2017/07/10)
-
- Stereoselective Synthesis of Alkenyl Silanes, Sulfones, Phosphine Oxides, and Nitroolefins by Radical C-S Bond Cleavage of Arylalkenyl Sulfides
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A radical-mediated approach has been introduced for the C-S bond activation of arylalkenyl sulfides. The protocol provides an efficient approach for the generation of various alkenes including alkenyl silanes, sulfones, phosphine oxides, and nitroolefins. In most cases, these radical substitutions are performed under metal-free conditions with stereospecificity.
- Lin, Ya-mei,Lu, Guo-ping,Wang, Rong-kang,Yi, Wen-bin
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supporting information
p. 1100 - 1103
(2017/03/15)
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- T-BuOK-mediated reductive addition of P(O)-H compounds to terminal alkynes forming β-arylphosphine oxides
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A novel and efficient t-BuOK-mediated reductive addition of P(O)-H compounds to terminal alkynes was developed. A variety of β-arylphosphine oxides including the valuable β-heteroarylphosphine oxides were produced in moderate to high yields under mild reaction conditions. This reaction may proceed via a tandem process involving regio-selective double addition and subsequent transfer hydrogenation.
- Zhang, Ji-Shu,Zhang, Jian-Qiu,Chen, Tieqiao,Han, Li-Biao
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supporting information
p. 5462 - 5467
(2017/07/12)
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- Solvent-controlled direct radical oxyphosphorylation of styrenes mediated by Manganese(III)
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Direct radical oxyphosphorylation of styrenes with diarylphosphine oxides and dialkyl phosphites mediated by Mn(OAc)3 is described. The solvent played a key role in this selective difunctionalization reaction.
- Zhang, Guo-Yu,Li, Cheng-Kun,Li, Da-Peng,Zeng, Run-Sheng,Shoberu, Adedamola,Zou, Jian-Ping
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p. 2972 - 2978
(2016/05/19)
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- Silver-catalyzed synthesis of 2-arylvinylphosphonates by cross-coupling of β-nitrostyrenes with: H -phosphites
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An efficient protocol for stereoselective synthesis of 2-arylvinylphosphonates has been developed via AgNO3-catalyzed cross-coupling of β-nitrostyrenes with dialkyl H-phosphites under mild conditions. By losing the nitro group of β-nitrostyrene
- Yuan, Jin-Wei,Yang, Liang-Ru,Mao, Pu,Qu, Ling-Bo
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p. 87058 - 87065
(2016/09/23)
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- Direct radical acetoxyphosphorylation of styrenes mediated by manganese(III)
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Direct radical acetoxyphosphorylation of styrenes mediated by Mn(OAc)3 with diphenylphosphine oxide and dialkyl phosphites was described, and a new type of difunctionalization of alkenes was achieved.
- Zhou, Shao-Fang,Li, Da-Peng,Liu, Kui,Zou, Jian-Ping,Asekun, Olayinka Taiwo
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p. 1214 - 1220
(2015/01/30)
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- Synthesis and properties of four-membered phosphorus heterocycles-2-Fluoro-1,2λ5-Oxaphosphetanes
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(Graphical Abstract) The preparation of four-membered phosphorus(V)-heterocycles, 2-fluoro-1,2λ5-oxaphosphetanes, by reaction of P-fluoroylides with carbonyl compounds is described. The reaction is stereoselective and leads preferentially to the formation of threo-1,2λ5-oxaphosphetanes. Oxaphosphetanes were isolated as individual compounds and their structures were confirmed by 1, 13C, and 31 NMR spectra. The fluoro-1,2λ5-oxaphosphetanes may be easily converted to various alkenylphosphonates: allyl- or vinylphosphonates. This reaction represents a good method for the preparation of phosphorylated alkenes.
- Kolodiazhna, Anastasia O.,Kolodiazhnyi, Oleg I.
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p. 2232 - 2245
(2015/12/23)
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- Catalytic Asymmetric Synthesis of Phosphine Boronates
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The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds. Ambiphilic phosphine boronate esters are obtained by the asymmetric boration of α,β-unsaturated phosphine oxides with a copper/bisphosphine catalyst in good yields and high enantioselectivity. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds.
- Hornillos, Valentín,Vila, Carlos,Otten, Edwin,Feringa, Ben L.
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supporting information
p. 7867 - 7871
(2015/07/01)
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- Stereoselective synthesis of vinylphosphonates and phosphine oxides via silver-catalyzed phosphorylation of styrenes
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An efficient and stereoselective synthesis of vinylphosphonates and phosphine oxides was developed starting from styrenes using AgNO3 as the catalyst and K2S2O8 as the oxidant. The success of the reaction was fo
- Gui, Qingwen,Hu, Liang,Chen, Xiang,Liu, Jidan,Tan, Ze
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supporting information
p. 13922 - 13924
(2015/09/07)
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- Nickel-catalyzed decarboxylative C-P cross-coupling of alkenyl acids with P(O)H compounds
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The first nickel-catalyzed decarboxylative C-P coupling of a wide range of alkenyl acids with various P(O)H compounds, especially for H-phosphonates, has been developed, affording a versatile and efficient tool for the preparation of valuable (E)-1-alkeny
- Wu, Yile,Liu, Liu Leo,Yan, Kaili,Xu, Pengxiang,Gao, Yuxing,Zhao, Yufen
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p. 8118 - 8127
(2015/03/18)
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- Copper-catalyzed decarboxylative C-P cross-coupling of alkynyl acids with H-phosphine oxides: A facile and selective synthesis of (E)-1-alkenylphosphine oxides
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A novel and efficient copper-catalyzed decarboxylative cross-coupling of alkynyl acids for the stereoselective synthesis of E-alkenylphosphine oxides has been developed. In the presence of 10 mol % of CuCl without added ligand, base, and additive, various alkynyl acids reacted with H-phosphine oxides to afford E-alkenylphosphine oxides with operational simplicity, broad substrate scope, and the stereoselectivity for E-isomers.
- Hu, Gaobo,Gao, Yuxing,Zhao, Yufen
-
supporting information
p. 4464 - 4467
(2015/01/08)
-
- Experimental and theoretical studies on nickel-zinc-catalyzed cross-coupling of gem-dibromoalkenes with P(O)-H compounds
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A new stereoselective one-pot protocol for the preparation of E-alkenyl-phosphorus compounds under catalysis of an inexpensive nickel-zinc catalyst system has been developed, which provides a potential useful method for C-P bond formation. 31P NMR spectrum and density functional theory calculations were performed to study the reaction mechanism.
- Liu, Liu,Lv, Ye,Wu, Yile,Gao, Xiang,Zeng, Zhiping,Gao, Yuxing,Tang, Guo,Zhao, Yufen
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p. 2322 - 2326
(2014/01/06)
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- Copper (II)-catalyzed regio- and stereoselective addition of H/P(O)R 2 to alkynes
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Cu(acac)2 is the new universal catalyst for β-E regio- and stereoselective syn-addition of the H-P(O)-bond of diphenylphosphine oxide, H-phosphinates, dialkylphosphites to various alkynes in the synthesis of P(O)-containing alkenes. Without additives and ligands Cu(II)-compounds showed better results than CuI or Ni(acac)2. The catalytic system developed is tolerant to typical organic functional groups present in the alkynes and to the nature of different substituents in the H-P(O)-compounds.
- Trostyanskaya, Inna G.,Beletskaya, Irina P.
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p. 2556 - 2562
(2014/04/03)
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- Selective addition of P(O)H bonds to alkynes catalyzed by transition metals immobilized on polystyrene-bound triphenylphosphine
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Addition of P(O)H bonds to alkynes catalyzed by transition metals (Rh, Pd, and Ni) immobilized on polystyrene-bound triphenylphosphine proceeded efficiently to afford high yields of the addition products with high regioselectivity. The immobilized catalys
- Chen, Tieqiao,Zhou, Yongbo,Guo, Cancheng,Han, Li-Biao
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p. 1065 - 1067
(2013/09/24)
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- Nickel(II)-magnesium-catalyzed cross-coupling of 1,1-dibromo-1-alkenes with diphenylphosphine oxide: One-pot synthesis of (E)-1-alkenylphosphine oxides or bisphosphine oxides
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A novel nickel(II)-magnesium-mediated cross-coupling of diphenylphosphine oxide with a variety of 1,1-dibromo-1-alkenes has been developed, which provides a powerful and general methodology for the stereoselective synthesis of various (E)-1-alkenylphosphine oxides or bisphosphine oxides, with operational simplicity of the procedure, good to high yields and broad substrate applicability. Mechanistic studies reveal that the reaction might involve a Hirao reduction, cross-coupling and Michael addition. Copyright
- Liu, Liu,Wang, Yulei,Zeng, Zhiping,Xu, Pengxiang,Gao, Yuxing,Yin, Yingwu,Zhao, Yufen
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supporting information
p. 659 - 666
(2013/04/10)
-
- Highly regio- and stereoselective hydrophosphinylation of acetylenes with diphenylphosphine oxide catalyzed by immobilization of rhodium in MCM-41
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Highly regio- and stereoselective hydrophosphinylation of a wide range of acetylenes with diphenylphosphine oxide was achieved in toluene at 70 °C in the presence of 2 mol% of an MCM-41-immobilized bidentate phosphine rhodium complex [MCM-41-2P-RhCl(PPhs
- Huang, Yixiang,Hao, Wenyan,Ding, Guodong,Cai, Ming-Zhong
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experimental part
p. 141 - 146
(2012/09/07)
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- Diphosphino-functionalized MCM-41-immobilized rhodium complex: A highly efficient and recyclable catalyst for the hydrophosphinylation of terminal alkynes
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Diphosphino-functionalized MCM-41-immobilized rhodium complex (MCM-41-2P-RhCl3) was conveniently synthesized from commercially available and cheap γ-aminopropyltriethoxysilane via immobilization on mesoporous MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that this heterogeneous rhodium complex is a highly efficient catalyst for the hydrophosphinylation of terminal alkynes with diphenylphosphine oxide and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.
- Yao, Fang,Peng, Jian,Hao, Wenyan,Cai, Mingzhong
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experimental part
p. 803 - 808
(2012/09/07)
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- Copper-catalyzed C-P coupling through decarboxylation
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An acid for a phosphine: A versatile protocol for preparation of various di(phenyl)phosphoryl oxides was developed by copper-catalyzed decarboxylative coupling of alkenyl, alkynyl carboxylic acids, and N-benzylproline, respectively, with R2P(O)
- Hu, Jie,Zhao, Ning,Yang, Bin,Wang, Ge,Guo, Li-Na,Liang, Yong-Min,Yang, Shang-Dong
-
supporting information; experimental part
p. 5516 - 5521
(2011/06/21)
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- Rhodium-catalyzed anti-markovnikov-type hydrophosphination of terminal alkynes with diphosphines and hydrosilanes in the presence of oxygen
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A novel rhodium(I)-catalyzed hydrophosphination of terminal alkynes with diphosphines and hydrosilanes takes place regioselectively in the presence of small amounts of oxygen. After air-oxidation during workups, the corresponding anti-Markovnikov-type vinylic phosphine oxides were obtained in good yields. Copyright Taylor & Francis Group.
- Kawaguchi, Shin-Ichi,Kotani, Mao,Ohe, Takashi,Nagata, Shoko,Nomoto, Akihiro,Sonoda, Motohiro,Ogawa, Akiya
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experimental part
p. 1090 - 1097
(2010/08/06)
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- Regio- and stereospecific cleavage of stannyloxiranes with lithium diphenylphosphide
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Unsubstituted or C-substituted stannyloxiranes reacted stereospecifically with lithium diphenylphosphide to give either β-hydroxyphosphane oxides resulting from α-opening or β-phosphanyl ketones by β-opening. Furthermore, the reactivities of distannyloxir
- Gonzalez-Nogal, Ana M.,Cuadrado, Purification,Sarmentero, M. Angeles
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scheme or table
p. 850 - 859
(2009/07/17)
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- Rhodium-catalyzed reaction of 1-alkynylphosphines with water yielding (E')-l-alkenylphosphine oxides
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Treatment of 1-alkynylphosphines with a rhodium catalyst in l,4-dioxane/H20 at reflux provides (E)-1 -alkenyl-phosphine oxides in good yields with perfect stereoselectivity. The reaction proceeds as follows. Oxidative addition of 1 -alkynylphosphine to rhodium followed by hydrolysis yields the corresponding terminal alkyne and diphenylphos-phine oxide. Rhodium-catalyzed hydrophosphinylation of the terminal alkyne then proceeds to afford (E)-1 -alkenylphosphine oxide.
- Kondoh, Azusa,Yorimitsu, Hideki,Oshima, Koichiro
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experimental part
p. 502 - 505
(2009/04/07)
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- Palladium-complex-catalyzed regioselective Markovnikov addition reaction and dehydrogenative double phosphinylation to terminal alkynes with diphenylphosphine oxide
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Palladium-1,2-bis(diphenylphosphino)ethane complex catalyzes regioselective Markovnikov addition of diphenylphosphine oxide to terminal alkynes in propionitrile, while the use of triarylphopshines, di(o-tolyl)phenylphosphine in particular, as the ligand l
- Dobashi, Naotomo,Fuse, Kouichiro,Hoshino, Takako,Kanada, Jun,Kashiwabara, Taigo,Kobata, Chihiro,Nune, Satish Kumar,Tanaka, Masato
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p. 4669 - 4673
(2008/03/12)
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- Copper-catalyzed addition of H-phosphine oxides to alkynes forming alkenylphosphine oxides
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We have developed efficient copper-catalyzed additions of P(O)H compounds to alkynes, and the reactions provided the regio- and stereoselective E-alkenylphosphine oxides under catalysis of the commercially available and inexpensive copper catalyst system
- Niu, Mingyu,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 272 - 274
(2007/10/03)
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- Efficient and Selective Nickel-Catalyzed Addition of H-P(O) and H-S Bonds to Alkynes
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The cheap nickel catalysts are more reactive than the corresponding noble metal catalysts in the catalytic additions of a variety of P(O)-H bonds and an S-H bond to alkynes, affording regio- and stereoselectively both the Markovnikov and the anti-Markovnikov adducts, respectively, in high yields. A related five-coordinate hydrido nickel complex in the catalysis is successfully isolated, which can react readily with an alkyne to give the addition products. Copyright
- Han, Li-Biao,Zhang, Chen,Yazawa, Hideaki,Shimada, Shigeru
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p. 5080 - 5081
(2007/10/03)
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- Radical addition reactions of chiral phosphorus hydrides
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Intermolecular radical addition of a (1R,2R,3S,5R)-(-)-pinanediol-derived thiophosphite leads to the diastereoselective formation of organophosphorus adducts. Addition of the intermediate phosphonothioyl radical to electron-rich alkenes or alkynes occurs
- Jessop, Christopher M.,Parsons, Andrew F.,Routledge, Anne,Irvine, Derek J.
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p. 2849 - 2851
(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 lanthanide(II)-imine complexes and their use in carbon-carbon and carbon-nitrogen unsaturated bond transformation
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Ytterbium and samarium metals reduced aromatic ketimines to give directly divalent azalanthanacyclopropane complexes 1 quantitatively, the structure of which was characterized by X-ray analysis. The imine complexes 1 catalyzed dehydrogenative silylation of terminal alkynes, hydrosilylation of imines and alkenes, and intermolecular hydrophosphination of alkynes. Moreover, dehydrogenative double silylation of conjugated dienes was achieved with 1.
- Takaki, Ken,Komeyama, Kimihiro,Takehira, Katsuomi
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p. 10381 - 10395
(2007/10/03)
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- PROCESS FOR PREPARATION OF ALKENYLPHOSPHINE OXIDES OR ALKENYLPHOSPHINIC ACID ESTERS
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A novel process for preparation of alkenylphosphine oxides or alkenylphosphinic acid esters provided by which the objective compounds can be easily, safely and efficiently synthesized and easily separated and purified with little formation of by-products
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- t-BuOK-catalyzed addition phosphines to functionalized alkenes: A convenient synthesis of polyfunctional phosphine derivatives
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The use of t-BuOK in DMSO allows a smooth addition of Ph2PH, Cy2PH and Ph2P(O)H to various functionalized alkenes leading to polyfunctional phosphines in good yields. This method has been used to prepare precursors for P,P- and P,N-ligands.
- Bunlaksananusorn, Tanasri,Knochel, Paul
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p. 5817 - 5819
(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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- Intermolecular hydrophosphination of alkynes and related carbon-carbon multiple bonds catalyzed by ytterbium-imine complexes
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Catalytic intermolecular hydrophosphination of alkynes with Ph2PH has been achieved by using a ytterbium-imine complex, [Yb(η2-Ph2CNPh)(hmpa)6]. Thus, both terminal and internal alkynes were converted in high yi
- Takaki, Ken,Takeda, Mitsuhiro,Koshoji, Go,Shishido, Tetsuya,Takehira, Katsuomi
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p. 6357 - 6360
(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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