- An expedient access to γ-ketophosphine chalcogenides via the chemo-and regioselective addition of secondary phosphine chalcogenides to β,γ-ethylenic ketones
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γ-Ketophosphine chalcogenides, precursors for plethora of novel functionalized phosphine chalcogenides and phosphines, are synthesized by chemo-and regioselective addition of secondary phosphine chalcogenides to β,γ-ethylenic ketones under catalyst-and so
- Artem’Ev, Alexander V.,Malysheva, Svetlana F.,Belogorlova, Nataliya A.,Protzuk, Nadezhda I.,Albanov, Alexander I.,Bagryanskaya, Irina Y.,Schmidt, Elena Y.,Gusarova, Nina K.,Trofimov, Boris A.
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- 5,5'-Diamino-BIPHEP ligands bearing small selector units for non-covalent binding of chiral analytes in solution
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A dynamic axially chiral BIPHEP-ligand with 3,5-dichlorobenzoyl amide selector units for non-covalent binding of phenylalanine derivatives has been developed. Interaction studies in solution were performed with rhodium(i) complexes under exclusion of the metal being involved in binding. (Rax, SPhe) and (Sax, SPhe) adducts were observed as significantly separated species in NMR spectroscopy.
- Storch,Siebert,Rominger,Trapp
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- Metal-Free, Visible Light-Photocatalyzed Synthesis of Benzo[b]phosphole Oxides: Synthetic and Mechanistic Investigations
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Highly functionalized benzo[b]phosphole oxides were synthesized from reactions of arylphosphine oxides with alkynes under photocatalytic conditions by using eosin Y as the catalyst and N-ethoxy-2-methylpyridinium tetrafluoroborate as the oxidant. The reac
- Quint, Valentin,Morlet-Savary, Fabrice,Lohier, Jean-Fran?ois,Lalevée, Jacques,Gaumont, Annie-Claude,Lakhdar, Sami
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- Cycloadditions of 3,4-dihydro-2H-pyrrole N-oxide with thioketones and a selenoketone
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Cycloadditions of 2-diphenylphosphinoyl-2-methyl-3,4-dihydro-2H-pyrrole N-oxide (DPhPMPO), 3,4-dihydro-2H-pyrrole N-oxide having a diphenylphosphinoyl group at the C2 position with thioketones afforded the corresponding 1,4,2-oxathiazolidines. Dissociation constants of these 5-membered ring products were determined. The cycloadducts were stabilized by the diphenylphosphinoyl group. The reaction of DPhPMPO with di-tert-butyl selenoketone gave the corresponding selenoamide under microwave irradiation. The formation of the selenoamide indicated that the cycloaddition of DPhPMPO with the selenoketone analogue also proceeded through the formation of the corresponding 5-membered ring product.
- Shioji, Kosei,Matsumoto, Akio,Takao, Masahiko,Kurauchi, Yoshimitsu,Shigetomi, Toshiyuki,Yokomori, Yoshinobu,Okuma, Kentaro
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- Extraction and coordination behavior of diphenyl hydrogen phosphine oxide towards actinides
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Extraction behavior of some selected actinides like U(VI), Th(IV), and Am(III) was investigated with three different H-phosphine oxides, viz. diphenyl hydrogen phosphine oxide (DPhPO), dihexyl hydrogen phosphine oxide (DHePO) and diphenyl phosphite (DPP).
- Das, Dhrubajyoti,Gopakumar, Gopinadhanpillai,Brahmmananda Rao,Sivaraman,Sivaramakrishna, Akella,Vijayakrishna, Kari
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- Conversion of α‐hydroxy(2,4,6‐trimethylbenzyl)diphenylphosphine oxide to TPO: oxidation vs decomposition
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This study details the oxidation of α-hydroxy(2,4,6-trimethylbenzyl)diphenylphosphine oxide (α-HDPO) to diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) by choosing the proper MnO2 as oxidant. In addition, the equilibrium of α-HDPO and 2,4
- Zhang, Jian-Qiu,Zhao, Jingzhuo,Li, Chunya,Ye, Jingjing,Han, Li-Biao
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- Photochemistry and Photophysics of (1-Naphthoyl)diphenylphosphine Oxide
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(l-Naphthoyl)diphenylphosphine oxide (1) was synthesized and characterized and its photochemistry investigated using emission spectroscopy, pulse radiolysis, and nanosecond laser flash photolysis. Fluorescence quantum yields are low in aprotic polar and nonpolar solvents. In methanol, as a result of hydrogen-bonding, change of S1 from an n,π* state to a π,π* state leads to the decrease in the rate constant for intersystem crossing and results, finally, in an increase in fluorescence. Preferential solvation was evaluated using the ET indicator "Reichardt's dye" (RD). ETN values were determined by gradually increasing the concentrations of methanol in methanol/acetonitrile mixtures. Fluorescence quantum yields correlate with the ETN values. Photolysis of 1 yields diphenyl[l-naphthoyl)oxy]phosphine (6), formed mainly via cage recombination of radicals. No radicals were detected by either nanosecond laser flash photolysis or pulse radiolysis of 1 in aprotic solvents. However, photolysis in methanol yields radicals when 1 is excited at 266 nm. The phosphinoyl radical can be quenched by either methyl methacrylate (MMA) or oxygen (kq = 5.0 × 107 and 5.3 × 108 M-1 s-1, respectively). Such radical generation most likely results from the singlet excited state.
- Zhao, Ningning,Strehmel, Bernd,Gorman, Anthony A.,Hamblett, Ian,Neckers, Douglas C.
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- Synthesis of novel N,O-macrocyclic ligands, functionalized by phosphine oxide groups
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[Figure not available: see fulltext.] As a result of the implementation of two approaches, the Pudovik reaction (the reaction of macrocyclic azomethines with secondary phosphine oxides) and the Kabachnik–Fields reaction (three-component one-pot process involving dialdehydes, diamines, and secondary phosphine oxides), novel N,O-containing macrocyclic ligands with phosphine oxide groups were first obtained. The synthesized macrocycles are a kind of α-aminophosphoryl compounds that can be used in the synthesis of supramolecular systems.
- Alexandrova, Elena А.,Lotsman, Kristina А.,Lyssenko, Konstantin А.,Trishin, Yuri G.
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- Phosphinoyl radicals: Structure and reactivity. A laser flash photolysis and time-resolved ESR investigation
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The photochemistry of a series of bis(acyl)phosphine oxides and the rate constants of the reactions of their phosphorus radicals with n-butylacrylate, thiophenol, bromotrichloromethane, oxygen, and methyl viologen have been investigated by laser flash pho
- Jockusch, Steffen,Turro, Nicholas J.
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- Catalytic Cleavage of Unactivated C(aryl)-P Bonds by Chromium
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We describe here the coupling to transform aryl phosphine derivatives by the cleavage of unactivated C(aryl)-P bonds with chromium catalysis, allowing us to achieve the reaction with alkyl bromides and arylmagnesium reagents under mild conditions. Mechani
- Ling, Liang,Luo, Meiming,Tang, Jinghua,Yuan, Shuqing,Zeng, Xiaoming
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supporting information
p. 1581 - 1586
(2022/03/14)
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- Electrochemical Oxidative C–H Phosphonylation of thiazole derivatives in ambient conditions
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We herein report a direct electrochemical dehydrogenative C–H phosphonylation of thiazoles derivatives with H2 evolution. Employing electricity as the green and sole oxidant, cheap metal as electrode, the anodic oxidation together with cathodic hydrogen evolution process provides a green and efficient strategy for C–H phosphonylation. A diverse range of phosphorus products were constructed under external metal and oxidant-free conditions at ambient temperature, featuring atom economy, simple operation and wide reaction scope.
- Li, Yang,Wu, Lei,Yang, Yan-Tong,Zhu, Jie,Zhu, Peng-Wei
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- Rh-Catalyzed Regio- and Enantioselective Allylic Phosphinylation
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Transition-metal-catalyzed branched and enantioselective allylic substitution of monosubstituted precursors with carbon, nitrogen, oxygen, sulfur, and fluoride nucleophiles has been well-established. However, such a selective carbon-phosphorus bond formation has not been realized probably due to the catalyst deactivation by the strong coordinating nature of phosphinylating reagents. Herein, we report a Rh-catalyzed highly regio- and enantioselective synthesis of allylic phosphine oxides in the presence of a chiral bisoxazoline-phosphine ligand. The application of α-hydroxylalkylphosphine oxides to keep the low concentration of the secondary phosphine oxides is essential for the high yields. The addition of diphenyl phosphoric acid was found to not only activate allylic alcohols but also accelerate the carbon-phosphorus bond formation.
- Li, Bing,Li, Changkun,Liu, Min,Rehman, Sajid Ur
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supporting information
p. 2893 - 2898
(2022/03/02)
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- Visible-light-induced ligand to metal charge transfer excitation enabled phosphorylation of aryl halides
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We herein described a visible light induced nickel(II)-catalyzed cross-coupling of secondary phosphine oxides with aryl halides. The Ni(I)species and chlorine atom radical Cl˙ were generatedviathe ligand to metal charge transfer (LMCT) process of the NiCl2(PPh3)2, which allows nickel(IV)-phosphorus speciesin situformation, giving various tertiary phosphine oxides under photocatalyst-free conditions.
- Hou, Hong,Zhou, Bing,Wang, Jiawei,Sun, Duhao,Yu, Huaguang,Chen, Xiaoyun,Han, Ying,Shi, Yaocheng,Yan, Chaoguo,Zhu, Shaoqun
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supporting information
p. 5702 - 5705
(2021/06/16)
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- AlCl3-catalyzed C-H p hosphination of benzene: A mechanistic study
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The characteristics of the reaction for the preparation of dichlorophenylphosphine (DCPP) via benzene and PCl3 in the presence of AlCl3 were studied. Some unique characteristics were observed when a catalytic amount of AlCl3 was used. Namely, more than one mole of DCPP was obtained per mole AlCl3, the reaction solution was layered, and DCPP could be directly separated. Our mechanistic study showed that benzene reacted with PCl3 to form DCPP-AlCl3, and DCPP-AlCl3 dissociated into DCPP and AlCl3, continuing to catalyze this reaction. This resulted in the high catalytic efficiency of AlCl3. The layering of the reaction solution was caused by the immiscibility of DCPP-AlCl3 with the raw materials, greatly facilitating the dissociation process of DCPP-AlCl3. The formation of diphenylphosphorus chloride (DPC) was due to a continuous Friedel-Crafts reaction between DCPP and benzene. DPC cooperated with AlCl3 to form the stable coordination compound DPC-AlCl3 that did not dissociate and was responsible for the deactivation of AlCl3.
- Duan, Haodong,Gao, Jun,Guo, Ge,Han, Yuxi,Leng, Kangwei,Li, Xinjin,Wang, Zhongwei,Xu, Xiaolei,Yu, Qing
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- Monoacylphosphine oxides with substituents in the phosphonyl moiety as Norrish I photoinitiators: Synthesis, photoinitiattion properties and mechanism
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In order to study the effect of the substituents in the phosphonyl moiety of monoacylphosphine oxide (MAPO) on its stability and initiation performance, (2,4,6-trimethylphenyl)(phenyl)(benzoyl)phosphine oxide (TMBPO), (4-tolyl)(phenyl)(2,4,6-trimethylbenzoyl)phosphine oxide (4-MTPO) and (2,4-xylyl)(phenyl)(2,4,6-trimethylbenzoyl)phosphine oxide (2,4-DMTPO) were designed and prepared. Studies on TMBPO showed that the introduction of methyl groups into the phosphonyl moiety of MAPO significantly enhanced its stability and light absorption abilities. The photopolymerization of trimethylolpropane triacrylate (TMPTA) showed that the initiation efficiency of 4-MTPO and 2,4-DMTPO were higher than that of TPO, regardless of whether it was initiated upon LED at 385 nm or 420 nm. In addition, the migration rates of 4-MTPO and 2,4-DMTPO in cured TMPTA were approximately 1/2 and 1/4 that of TPO, respectively.
- Duan, Haodong,Gao, Jun,Han, Yuxi,Leng, Kangwei,Li, Qianmin,Liu, Dayong,Wang, Zhongwei,Xu, Xiaolei,Yu, Qing
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- Synthesis of tertiary phosphine oxides by alkaline hydrolysis of quaternary phosphonium zwitterions using excess t-BuOK and stoichiometric water
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Hydrolysis of quaternary arylphosphonium zwitterions bearing COO? and those in situ generated from the corresponding salts bearing Ac or OH at the aryl ring by using excess t-BuOK and stoichiometric water affords tertiary arylphosphine oxides in moderate to excellent yield, in contrast to hydrolysis of these zwittertion or salts in aqueous NaOH that mainly provides phosphine oxides with the loss of the aryl group. Under the t-BuOK/water conditions, hydrolysis of carbonyl stabilized ylides Ph3P = CHCOR (R = Ph, Me, and OEt), which partially exist as phosphonium enolates, prefers to produce Ph2P(O)CH2COR. Further reduction of Ph2P(O)CH2COMe by PhSiH3 allows the preparation of Ph2PCH2COMe in 43% yield.
- Zhong, Chun-Hong,Huang, Wenhua
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supporting information
p. 1537 - 1546
(2021/01/07)
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- Organic photoredox catalytic α-C(sp3)-H phosphorylation of saturated: Aza -heterocycles
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A metal-free C(sp3)-H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Br?nsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D-A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.
- Yi, Ming-Jun,Xiao, Teng-Fei,Li, Wen-Hui,Zhang, Yi-Fan,Yan, Pen-Ji,Zhang, Baoxin,Xu, Peng-Fei,Xu, Guo-Qiang
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supporting information
p. 13158 - 13161
(2021/12/16)
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- Highly Enantioselective Synthesis of Phosphorus-Containing ?-Benzosultams by Bifunctional Phosphonium Salt-Promoted Hydrophosphonylation
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?-Benzosultam derivatives are potential drug candidates with diverse biological activities. A series of chiral ?-benzosultams bearing phosphorus functionalities was synthesized by catalytic asymmetric hydrophosphonylation in the presence of a bifunctional phosphonium salt catalyst. The desired hydrophosphonylation products were obtained in good yields with high enantioselectivities, and scale-up reactions and further derivations were successfully accomplished. Some control experiments were also conducted to elucidate the plausible reaction mechanism of this chemical transformation.
- Zhang, Song,Feng, Zhenghuai,Jiang, Chunhui,Yu, Xiaojun,Pan, Jianke,Du, Juan,Jiang, Zhiyu,Chen, Yuan,Wang, Tianli
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supporting information
p. 11285 - 11290
(2021/07/02)
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- Manganese-Promoted Regioselective Direct C3-Phosphinoylation of 2-Pyridones
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A highly efficient and regioselective manganese-induced radical oxidative direct C?P bond formation between 2-pyridones and secondary phosphine oxides was developed. The C3-selective phosphinoylation was conveniently achieved through a combination of substoichiometric manganese and persulfate oxidant under mild conditions. Various 3-phosphinoylated pyridone products can be obtained in moderate to high yields. Preliminary mechanistic studies suggest that the reaction is likely to involve a radical pathway induced by catalytically active Mn3+ species.
- Chantarojsiri, Teera,Kittikool, Tanakorn,Phakdeeyothin, Kunita,Yotphan, Sirilata
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supporting information
p. 3071 - 3078
(2021/07/22)
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- Copper-Catalyzed C?P Cross-Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with in situ Halogen Exchange
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An efficient protocol for concurrent tandem halogen exchange/C?P cross-coupling of cycloalkenyl bromides and secondary phosphine oxides has been developed. The catalytic system is based on cheap and air-stable copper(I) iodide as the precatalyst, commercially available N,N’-dimethylethylenediamine as the ligand, and Cs2CO3 or K2CO3 as the base. The use of sodium iodide as an additive reduces the excessive use of organic bromides to near-stoichiometric by promoting the in situ transformation to the corresponding iodides. Diarylphosphine oxides undergo cycloalkenylation with 35–99 % yields and dicyclohexylphosphine oxide with 30–53 % yields. In the case of acyclic alkenyl bromides the cross-coupling products undergo conjugate addition of diphenylphosphine oxide and satisfying yields are observed only for internal olefins. In the case of aryl bromides satisfying yields (43–72 %) are observed only for sterically unhindered arenes or arenes possessing an ortho-directing group. Cycloalkenylphosphine oxides prepared in the cross-coupling reaction undergo base-catalyzed and base-promoted conjugate addition to give bis(phosphinoyl)cycloalkanes.
- Stankevi?, Marek,Wo?nicki, Pawe?
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supporting information
p. 3484 - 3491
(2021/07/22)
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- Ruthenium-catalyzed regio- And site-selective: Ortho C-H borylation of phenol derivatives
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Efficient synthesis of o-borylphenols is achieved through the Ru-catalyzed regio- and site-selective sp2 C-H borylation of aryl diphenylphosphinites followed by removal of the phosphorus directing group. A successful application to aryl phosphites enables practical one-pot borylation of phenols, demonstrating high synthetic utility of this protocol.
- Homma, Yuki,Fukuda, Kazuishi,Iwasawa, Nobuharu,Takaya, Jun
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supporting information
p. 10710 - 10713
(2020/10/02)
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- Diaryl phosphine oxide compound containing substituent groups and preparation method thereof
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The invention discloses a diaryl phosphine oxide compound containing substituent groups and a preparation method of the diaryl phosphine oxide compound, the structural formula of the diaryl phosphineoxide compound is shown as (I), wherein R1 to R10 are independently selected from H, alkyl, halogen or halogen-substituted alkyl, and the halogen comprises F, Cl, Br and I. The preparation method comprises the following steps: adding aryl phosphine dichloride or a derivative thereof, aromatic hydrocarbon or a derivative thereof and a catalyst into a reaction flask, reacting for a certain period oftime under mild conditions, and dropwise adding into an ice-water mixture to hydrolyze after the reaction is completed, thereby obtaining the diaryl phosphine oxide compound. The preparation processhas the advantages of simple operation, mild reaction conditions, green and environment-friendly preparation process and the like. The diaryl phosphine oxide compound prepared by the method not only can be directly used for flame-retardant modification of epoxy resin, but also is an important raw material for synthesizing a novel acyl phosphine photoinitiator and a phosphorus-containing flame retardant.
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Paragraph 0039-0044
(2020/03/17)
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- Visible-light-driven metal-free aerobic synthesis of highly diastereoselective phosphinoylpyrroloindoles
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A visible-light-driven metal-free phosphorus radical mediated construction of 2-phosphinoyl-3H-pyrrolo[1,2,a]indoles is described. This mild tandem phosphinoylation/cyclization protocol utilizes air as a green oxidant and proceeds in a short span of time at room temperature with high functional group tolerance, and excellent chemo- A nd diastereoselectivity.
- Gorre, Ramesh,Enagandhula, Damodar,Balasubramanian, Sridhar,Akondi, Srirama Murthy
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supporting information
p. 1354 - 1358
(2020/03/03)
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- Direct and Scalable Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine
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The direct and scalable electroreduction of triphenylphosphine oxide (TPPO)-the stoichiometric byproduct of some of the most common synthetic organic reactions-to triphenylphosphine (TPP) remains an unmet challenge that would dramatically reduce the cost and waste associated with performing desirable reactions that are mediated by TPP on a large scale. This report details an electrochemical methodology for the single-step reduction of TPPO to TPP using an aluminum anode in combination with a supporting electrolyte that continuously regenerates a Lewis acid from the products of anodic oxidation. The resulting Lewis acid activates TPPO for reduction at mild potentials and promotes P-O over P-C bond cleavage to selectively form TPP over other byproducts. Finally, this robust methodology is applied to (i) the reduction of synthetically useful classes of phosphine oxides, (ii) the one-pot recycling of TPPO generated from a Wittig reaction, and (iii) the gram-scale reduction of TPPO at high concentration (1 M) with continuous product extraction and in flow at high current density.
- Manabe, Shuhei,Sevov, Christo S.,Wong, Curt M.
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p. 3024 - 3031
(2020/03/10)
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- Cobaloxime Catalysis for Enamine Phosphorylation with Hydrogen Evolution
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Direct phosphorylation of enamine and enamide with hydrogen evolution was realized via cobaloxime catalysis under visible-light irradiation. Control experiments and spectroscopic studies demonstrated a reductive quenching pathway of cobaloxime catalyst to produce phosphinoyl radical, which underwent cross-coupling with various enamines (and enamides) to give diverse β-phosphinoyl products in good to excellent yields. More interestingly, Z/E mixture of acyclic enamines could convert into single Z-products with good reactivity.
- Lei, Tao,Liang, Ge,Cheng, Yuan-Yuan,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
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supporting information
p. 5385 - 5389
(2020/07/08)
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- METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0088; 0094
(2020/05/02)
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- An Alternative Metal-Free Aerobic Oxidative Cross-Dehydrogenative Coupling of Sulfonyl Hydrazides with Secondary Phosphine Oxides
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An alternative metal-free, efficient and practical approach for the preparation of phosphinothioates is established via the aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides catalyzed by tetrabutylammonium iodide (TBAI) in the presence of atmospheric oxygen. The strategy provides an array of diverse phosphinothioates in good to excellent yields. Furthermore, two representative bioactive molecules are synthesized on up to gram scale by utilizing this method.
- Cheng, Feixiang,Liu, Jianjun,Liu, Teng,Yu, Rong,Zhang, Yanqiong
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p. 253 - 262
(2019/12/28)
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- Condensation reaction of homotrimethoxy benzoyl halides and diphenylphosphines and preparation of organic phosphine compounds
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The present invention relates to the field of organic phosphine functional new material chemicals, and a "one-pot" direct condensation reaction of trimethylbenzoyl halide and an equivalent thereof and diphenylphosphine oxide is disclosed for the first time. By using this reaction process technology, two organic phosphine compounds are prepared simultaneously or one of them is selectively prepared, that is, trimethylbenzoyldiphenylphosphine oxide and trimethylbenzyl alcohol diphenylphosphine oxide diphenylphosphonate. The process technology has outstanding low-cost economic competitiveness and environmentally friendly characteristics.
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Paragraph 0060-0061
(2020/03/17)
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- C-Alkyl-bis-phosphoryl chelating systems for the potential recovery of strategic metals
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Methylene-bis-phosphonic acid and derivatives are used as complexing agents, diagnostics, therapeutics and show interesting virustatic properties. We describe the syntheses of mono- and di-substituted bisphosphonates and mono- and disubstituted diethyl ((diphenylphosphoryl)methyl)phosphonate as possible chelating systems for the recovery of strategic metals.
- Babouri, Rachida,Halidou Dougourikoye, Abdoul Razak,Ilagouma, Amadou TidJani,Pirat, Jean-Luc,Virieux, David,Volle, Jean-No?l
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- Structure-based design, synthesis, and evaluation of the biological activity of novel phosphoroorganic small molecule IAP antagonists
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One of the strategies employed by novel anticancer therapies is to put the process of apoptosis back on track by blocking the interaction between inhibitor of apoptosis proteins (IAPs) and caspases. The activity of caspases is modulated by the caspases themselves in a caspase/procaspase proteolytic cascade and by their interaction with IAPs. Caspases can be released from the inhibitory influence of IAPs by proapoptotic proteins such as secondary mitochondrial activator of caspases (Smac) that share an IAP binding motif (IBM). The main purpose of the present study was the design and synthesis of phosphorus-based peptidyl antagonists of IAPs that mimic the endogenous Smac protein, which blocks the interaction between IAPs and caspases. Based on the structure of the IAP antagonist and recently reported thiadiazole derivatives, we designed and evaluated the biochemical properties of a series of phosphonic peptides bearing the N-Me-Ala-Val/Chg-Pro-OH motif (Chg: cyclohexylglycine). The ability of the obtained compounds to interact with the binding groove of the X-linked inhibitor of apoptosis protein baculovirus inhibitor of apoptosis protein repeat (XIAP BIR3) domain was examined by a fluorescence polarization assay, while their potential to induce autoubiquitination followed by proteasomal degradation of cellular IAP1 was examined using the MDA-MB-231 breast cancer cell line. The highest potency against BIR3 was observed among peptides containing C-terminal phosphonic phenylalanine analogs, which displayed nanomolar Ki values. Their antiproliferative potential as well as their proapoptotic action, manifested by an increase in caspase-3 activity, was examined using various cell lines.
- ?upicka-S?owik, Agnieszka,Psurski, Mateusz,Grzywa, Renata,Cuprych, Monika,Ciekot, Jaros?aw,Goldeman, Waldemar,Wojaczyńska, El?bieta,Wojaczyński, Jacek,Oleksyszyn, Józef,Sieńczyk, Marcin
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p. 1350 - 1364
(2020/04/24)
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- Preparation method of 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide
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The invention relates to a preparation method of 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide and particularly relates to a method, which comprises that phosphorus trichloride, benzene and aluminumtrichloride as raw materials undergo a reaction, the reaction product undergoes a hydrolysis reaction to produce diphenylphosphine oxide, diphenylphosphine oxide and 2, 4, 6-trimethylbenzoyl chloridedirectly undergo a reaction to produce 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide. The preparation method of TPO solves the problems that the raw materials are difficult to prepare, the cost ishigh, the reaction steps are many, and the yield is low. The preparation method is an eco-friendly preparation process.
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Page/Page column 4-6
(2019/02/13)
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- Rearrangement and redistribution reaction of Ph2PCH2TMS with PhAsCl2 or AsCl3
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The attempted synthesis of bis(diphenylphosphinomethyl) phenylarsane and tris(diphenylphosphinomethyl) arsane through condensation of chloro arsanes and diphenyl (trimethylsilylmethyl) phosphane yielded a number of side products originating from migratory and redox-reactions in addition to the targeted ligands. An unexpected, 1,3,4-phosphadiarssolan-1-ium salt was obtained and crystallographically characterized as an A-shaped chlorido adduct.
- Gupta, Arvind Kumar,Green, Joshua P.,Orthaber, Andreas
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p. 967 - 971
(2019/07/03)
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- Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
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Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
- Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
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supporting information
p. 2916 - 2922
(2019/06/18)
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- Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination
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Given the periodic relationship of phosphines and arsines, is remodeling the catalytic asymmetric hydrophosphination reaction an efficient manner to develop the corresponding hydroarsination reaction? Herein, a chiral PCP-Pd(ii) pincer complex adept at ge
- Tay, Wee Shan,Yang, Xiang-Yuan,Li, Yongxin,Pullarkat, Sumod A.,Leung, Pak-Hing
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supporting information
p. 4602 - 4610
(2019/04/05)
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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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supporting information
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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supporting information
p. 13941 - 13947
(2019/09/30)
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- Microwave-assisted synthesis of α-aminophosphine oxides
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Aminophosphine oxides and bis(phosphinoylmethyl)amines were synthesized by the microwave (MW)-assisted Kabachnik-Fields reaction of primary amines, paraformaldehyde and secondary phosphine oxides. The bisphosphines obtained after deoxygenation of the bis(phosphinoymethyl)amine derivatives were utilized in the synthesis of cyclic transition metal complexes.
- Tripolszky, Anna,Bálint, Erika,Keglevich, Gy?rgy
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p. 345 - 348
(2019/03/07)
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- Highly chemo- and regioselective C-P cross-coupling reaction of quinone imine ketals with Ar2P(O)H to construct: Ortho -amino triarylphosphine derivatives
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A highly chemo- and regioselective approach for the construction of ortho-amino triarylphosphine oxides has been achieved through a C-P cross-coupling reaction involving quinone imine ketals (QIKs) with Ar2P(O)H and catalyzed via a Lewis base. This alternative protocol provided a wide substrate scope with excellent yields (82-95%), and a variety of ortho-amino triarylphosphines were obtained with high yields (87-95%) via further reductive reaction. Furthermore, this reaction could be scaled-up and several synthetic transformations were accomplished for the construction of functionalized organophosphorus.
- Liu, Teng,Li, Yongqin,Cheng, Feixiang,Shen, Xianfu,Liu, Jianjun,Lin, Jun
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supporting information
p. 3536 - 3541
(2019/07/10)
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- Palladium-catalyzed phosphination and amination through C–H bond functionalization on biphenyl: Amido-substituent as directing group
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The formation of N-(2’-(diphenylphosphoryl)-[1,1′-biphenyl]-2-yl)-2,3,4,5,6-pentafluorobenzamide (3_eaaa) has been achieved through the palladium-catalyzed and Ag(I)-assisted C–H functionalization of N-([1,1′-biphenyl]-2-yl)-2,3,4,5,6-pentafluorobenzamide
- Kao, I-Hsiang,Wang, Ching-Yu,Chang, Yu-Chang,Wu, Chu-Lun,Chiu, Yu-Jen,Hong, Fung-E
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p. 387 - 397
(2019/01/04)
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- Synthesis of Phosphine Chalcogenides Under Solvent-Free Conditions Using a Rotary Ball Mill
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The mechanochemical technique of ball milling has been applied to the solventless and eco-friendly synthesis of chalcogenides (sulfide and selenide) of a variety of tertiary and aminophosphines. In most of the cases, the products are obtained in almost quantitative yields with high purity by applying a simple workup procedure without using chromatographic techniques or any other purification methods. The scope of this methodology was explored by using a range of phosphines (mono, di and tetra) to synthesize partial as well as mixed chalcogenides. The use of almost equimolar amounts of starting materials and the absence of any byproducts significantly simplifies the product isolation compared with the standard solution state reactions, thus providing a highly atom economic (100 %) method with an ideal E-factor (E = 0). The solid-state reactions were monitored by 31P{1H} NMR spectroscopy. The structures of some of the products are also confirmed by single-crystal X-ray analyses. Although most of the reactions were carried out on ca. 100-mg scale, the scaling up of the reaction did not affect the course of the reaction.
- Kumar, Rajnish,Kumar, Saurabh,Pandey, Madhusudan K.,Kashid, Vitthalrao S.,Radhakrishna, Latchupatula,Balakrishna, Maravanji S.
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p. 1028 - 1037
(2018/02/26)
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- Copper-catalyzed C–P cross-coupling of secondary phosphines with (hetero)aromatic bromide
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A novel and convenient approach to the synthesis of various tertiary phosphines via a copper-catalyzed cross-coupling of (hetero)aromatic bromide with secondary phosphines has been developed. The reaction employs cheap copper as the catalyst, 2,6-bis(N-methylaminomethyl)pyridine (L4) as a perfect ligand and KOtBu as a base; all reactions are carried out under argon atmosphere. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. Moreover, ten new tertiary phosphines were first reported in this process.
- Li, Chun-Jing,Lü, Jing,Zhang, Zhi-Xun,Zhou, Kun,Li, Yan,Qi, Guang-Hui
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p. 4547 - 4562
(2018/04/20)
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- Dearylation of arylphosphine oxides using a sodium hydride-iodide composite
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A new protocol for the dearylation of arylphosphine oxides was developed using sodium hydride (NaH) in the presence of lithium iodide (LiI). The transient sodium phosphinite could be functionalized with a range of electrophiles in a one-pot fashion.
- Tejo, Ciputra,Pang, Jia Hao,Ong, Derek Yiren,Oi, Miku,Uchiyama, Masanobu,Takita, Ryo,Chiba, Shunsuke
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supporting information
p. 1782 - 1785
(2018/02/21)
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- Chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder at room temperature
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A protocol for the chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder under an oxygen atmosphere is reported. This reaction proceeds efficiently to afford fully substituted unsymmetrical N-arylation phosphinamides at room temperature in excellent yields. Diverse unstable functional groups on the benzene ring of aryl boronic acids such as vinyl, formyl, acetyl, sulfonyl, acetylamino, cyano, nitro, and trifluoromethyl can be accommodated.
- Peng, Yao,Lei, Jian,Qiu, Renhua,Peng, Lingteng,Au, Chak-Tong,Yin, Shuang-Feng
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supporting information
p. 4065 - 4070
(2018/06/12)
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- Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
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Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
- Jia, Kunfang,Li, Junzhao,Chen, Yiyun
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supporting information
p. 3174 - 3177
(2018/02/09)
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- Regio- and Stereoselective Hydrophosphorylation of Ynamides for the Synthesis of β-Aminovinylphosphine Oxides
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A metal-free hydrophosphorylation of ynamides with diaryl phosphine oxides has been developed. A highly E-selective and β-regioselective hydrophosphorylation protocol has been established as a general method for the synthesis of diversely hydrophosphinylated products employing an in situ generated electrophilic phosphorus species. Deuterium incorporation experiments suggest that the amino phosphirenium intermediate undergoes a concerted ring-opening hydrolysis upon treatment with H2O to exclusively furnish β-aminovinylphosphine oxides.
- Huang, Hai,Zhu, Hongjun,Kang, Jun Yong
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supporting information
p. 2778 - 2781
(2018/05/22)
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- Asymmetric Covalent Triazine Framework for Enhanced Visible-Light Photoredox Catalysis via Energy Transfer Cascade
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Complex multiple-component semiconductor photocatalysts can be constructed that display enhanced catalytic efficiency via multiple charge and energy transfer, mimicking photosystems in nature. In contrast, the efficiency of single-component semiconductor photocatalysts is usually limited due to the fast recombination of the photogenerated excitons. Here, we report the design of an asymmetric covalent triazine framework as an efficient organic single-component semiconductor photocatalyst. Four different molecular donor–acceptor domains are obtained within the network, leading to enhanced photogenerated charge separation via an intramolecular energy transfer cascade. The photocatalytic efficiency of the asymmetric covalent triazine framework is superior to that of its symmetric counterparts; this was demonstrated by the visible-light-driven formation of benzophosphole oxides from diphenylphosphine oxide and diphenylacetylene.
- Huang, Wei,Byun, Jeehye,R?rich, Irina,Ramanan, Charusheela,Blom, Paul W. M.,Lu, Hao,Wang, Di,Caire da Silva, Lucas,Li, Run,Wang, Lei,Landfester, Katharina,Zhang, Kai A. I.
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supporting information
p. 8316 - 8320
(2018/06/29)
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- Quantum Yields over 80% Achieved in Luminescent Europium Complexes by Employing Diphenylphosphoryl Tridentate Ligands
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Four tridentate europium(III) complexes containing a diphenylphosphoryl group are prepared with strong bonding between the ligands and centered ion, convinced by crystal structures. Compared to their parent bidentate complexes, the tridentate complexes di
- Wei, Chen,Sun, Boxun,Cai, Zelun,Zhao, Zifeng,Tan, Yu,Yan, Weibo,Wei, Huibo,Liu, Zhiwei,Bian, Zuqiang,Huang, Chunhui
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supporting information
p. 7512 - 7515
(2018/07/13)
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- A Versatile Approach for Site-Specific Lysine Acylation in Proteins
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Using amber suppression in coordination with a mutant pyrrolysyl-tRNA synthetase-tRNAPylpair, azidonorleucine is genetically encoded in E. coli. Its genetic incorporation followed by traceless Staudinger ligation with a phosphinothioester allows the convenient synthesis of a protein with a site-specifically installed lysine acylation. By simply changing the phosphinothioester identity, any lysine acylation type could be introduced. Using this approach, we demonstrated that both lysine acetylation and lysine succinylation can be installed selectively in ubiquitin and synthesized histone H3 with succinylation at its K4 position (H3K4su). Using an H3K4su-H4 tetramer as a substrate, we further confirmed that Sirt5 is an active histone desuccinylase. Lysine succinylation is a recently identified post-translational modification. The reported technique makes it possible to explicate regulatory functions of this modification in proteins.
- Wang, Zhipeng A.,Kurra, Yadagiri,Wang, Xin,Zeng, Yu,Lee, Yan-Jiun,Sharma, Vangmayee,Lin, Hening,Dai, Susie Y.,Liu, Wenshe R.
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supporting information
p. 1643 - 1647
(2017/02/05)
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- Rhodium(III)-Catalyzed Enantiotopic C?H Activation Enables Access to P-Chiral Cyclic Phosphinamides
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Compounds with stereogenic phosphorus atoms are frequently used as ligands for transition-metal as well as organocatalysts. A direct catalytic enantioselective method for the synthesis of P-chiral compounds from easily accessible diaryl phosphinamides is presented. The use of rhodium(III) complexes equipped with a suitable atropochiral cyclopentadienyl ligand is shown to enable an enantiodetermining C?H activation step. Upon trapping with alkynes, a broad variety of cyclic phosphinamides with a stereogenic phosphorus(V) atom are formed in high yields and enantioselectivities. Moreover, these can be reduced enantiospecifically to P-chiral phosphorus(III) compounds.
- Sun, Yang,Cramer, Nicolai
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supporting information
p. 364 - 367
(2016/12/30)
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- C–H Bond Functionalization of 1,4-Benzoquinone by Silver-Mediated Regioselective Phosphination and Amination Reactions
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The one-pot synthesis of 2,5-bis(diarylphosphoryl)-3,6-bis(arylamino)cyclohexa-2,5-diene-1,4-diones has been achieved by AgI-mediated full C–H functionalization of 1,4-benzoquinone (BQ) through regioselective dual phosphination and amination reactions. BQ, diarylphosphine oxides [SPOs, Ar2PH(=O)], and imines reacted to give the products under mild conditions. 1,4-Naphthoquinone (NQ) could also be used instead of BQ. When aniline was used instead of the corresponding imine, a lower yield of the desired product was obtained. In the absence of Ag2CO3, hydrophosphinylation of the imine by the SPO occurred as a competitive side-reaction. AgI plays versatile roles in this reaction, as a mediator for facilitating the consecutive additions of Ar2P(=O)– and aniline to the related β-carbon atoms of BQ, as an oxidant of hydroquinone (HQ) intermediates to form the substituted BQ counterpart, and as an inhibitor of the hydrophosphinylation side-reaction of the imine by the SPO. The X-ray crystal structures of several new products have been determined. A reaction mechanism is also proposed based on the experimental results.
- Chang, Yu-Chang,Yuan, Pin-Ting,Hong, Fung-E
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p. 2441 - 2450
(2017/05/12)
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- Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization
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A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π-allylic nickel structures, these self-assembled complexes trigger catalytic hydrophosphinylation reactions. Addition of a Lewis acid B(C6F5)3 switches the reactivity towards migratory insertion and thus ethylene oligomerization through an unprecedented outer-sphere interaction with the coordinated SPO ligand. NMR experiments and X-ray analyses allowed for the observation of the formation of zwitterionic active species as well as their degradation pathway.
- Lhermet, Rudy,Moser, Emile,Jeanneau, Erwann,Olivier-Bourbigou, Hélène,Breuil, Pierre-Alain R.
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supporting information
p. 7433 - 7437
(2017/06/06)
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- Synthesis of P(O)-S organophosphorus compounds by dehydrogenative coupling reaction of P(O)H compounds with aryl thiols in the presence of base and air
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The synthesis method of P(O)-S organophosphorus compounds by dehydrogenative coupling reaction of P(O)H compounds and aryl thiols was developed. The reaction was carried in the presence of a base and air, and exhibited good characters such as metal-free,
- He, Wei,Hou, Xiao,Li, Xinjin,Song, Liang,Yu, Qing,Wang, Zhongwei
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supporting information
p. 3133 - 3138
(2017/05/08)
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- Insertion of phosphinidene complexes into the P-H bond of secondary phosphine oxides: A new version of the phospha-Wittig synthesis of P=C double bonds
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Terminal phosphinidene complexes [RP-W(CO)5], as generated at 60 °C in the presence of copper chloride from the appropriate 7-phosphanorbornadiene complexes, react with secondary phosphine oxides Ar2P(O)H to give the insertion products into the P-H bonds. After metalation with NaH, these products react with aldehydes to give the corresponding phosphaalkenes which are trapped by dimethylbutadiene.
- Hao, Yanwei,Wu, Di,Tian, Rongqiang,Duan, Zheng,Mathey, Fran?ois
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p. 891 - 893
(2016/01/15)
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- Zero-Valent Amino-Olefin Cobalt Complexes as Catalysts for Oxygen Atom Transfer Reactions from Nitrous Oxide
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The synthesis and characterization of several zero-valent cobalt complexes with a bis(olefin)-amino ligand is presented. Some of these complexes proved to be efficient catalysts for the selective oxidation of secondary and allylic phosphanes, as well as diphosphanes, even with a direct P?P bond. With 5 mol % catalyst loadings the oxidations proceed under mild conditions (25–70 °C, 7–22 h, 2 bar N2O) and afford good to excellent yields (65–98 %). In this process, the greenhouse gas N2O is catalytically converted into benign N2and added-value organophosphorus compounds, some of which are difficult to obtain otherwise.
- Gianetti, Thomas L.,Rodríguez-Lugo, Rafael E.,Harmer, Jeffrey R.,Trincado, Monica,Vogt, Matthias,Santiso-Quinones, Gustavo,Grützmacher, Hansj?rg
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supporting information
p. 15323 - 15328
(2016/12/06)
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- Organic phosphorus compound
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The invention discloses an organic phosphorus compound as shown in the figure and a preparation method thereof. The organic phosphorus compound has an acyl phosphine active functional group structure and can be used as an UV-light initiator. More important is that the compound aromatic ring is coupled with a tertiary amine structure, the ultraviolet absorption wavelength is moved to 380nm-395nm and the unsaturated monomer polymerization can be effectively triggered under the radiation of UV-LED lamp. Besides, the solubility of the compound in various resins and low polymer is excellent. The organic phosphorus compound is a novel acyl phosphine photoinitiator.
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Paragraph 0044; 0045; 0052; 0053; 0060; 0061
(2017/01/02)
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