51986-54-0Relevant academic research and scientific papers
Copper-Catalyzed C?P Cross-Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with in situ Halogen Exchange
Stankevi?, Marek,Wo?nicki, Pawe?
supporting information, p. 3484 - 3491 (2021/07/22)
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.
Functionalized triphenylphosphine oxide-based manganese(ii) complexes for luminescent printing
Huang, Xiaomeng,Liu, Shujuan,Meng, Haixing,Qin, Yanyan,She, Pengfei,Zhao, Qiang
, p. 8831 - 8836 (2021/07/02)
Three novel neutral manganese(ii) complexes(TPhPONMe2)2MnBr2,(TPhPOOMe)2MnBr2, and(TPhPOCF3)2MnBr2have been designed and synthesized based on a functionalized Ph3PO ligand. These structures are clarified by single crystal X-ray diffraction analysis, which reveals that they crystallize in centrosymmetric space groups and feature an isolated mononuclear structure with Mn2+in a tetrahedral environment. The photoluminescence spectra and emission lifetime decay curves of three manganese(ii) complexes show distinct green emission (λem= 498-512 nm) and phosphorescence lifetime (τ= 362.0-663.0 μs). The results of DFT calculations indicate that the energy levels of(TPhPONMe2)2MnBr2and(TPhPOOMe)2MnBr2are higher than that of(TPhPOCF3)2MnBr2due to the electron-donating effect of the NMe2or OMe group, which explains the blue-shift of the emission wavelength and the increase of emission lifetime. Furthermore, the prepared neutral manganese(ii) complexes can be used for high-resolution luminescent printing.
Novel neutral monodentate chelated manganese complex as well as preparation method and application thereof
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, (2020/10/20)
The invention discloses a novel neutral monodentate chelated manganese complex. Different electron donating and withdrawing substituents, such as N (Me) 2, OMe, CF3, OCF3, Cl, F, CN and Br, are introduced to a triphenylphosphine oxide ligand, so that the emission energy level and the luminescence life of the manganese complex can be easily adjusted, and the luminescence property of a material is further changed; and besides, information storage and protection can be realized by utilizing the neutral manganese complex.
Visible-light-induced ligand-free RuCl3 catalyzed C-H phosphorylation in water
Gou, Xue-Ya,Zhang, Bo-Sheng,Wang, Xin-Gang,Shi, Wei-Yu,Liu, Hong-Chao,An, Yang,Zhang, Zhe,Liang, Yong-Min
supporting information, p. 4704 - 4707 (2020/05/22)
Visible-light-induced C-H phosphorylation of para-CAr-H and heteroarenes was realized using cost-effective RuCl3 as a catalyst. The reaction conditions are green and environmentally friendly, using water as a solvent at room temperature and without ligands. A broad range of highly functional organophosphorus compounds were obtained via a cross-dehydrogenation-coupling (CDC) reaction. In addition, we also proved that RuCl3 is a photocatalyst via its absorption spectrum and on/off light experiments.
Visible-light-mediated semi-heterogeneous black TiO2/nickel dual catalytic C (sp2)-P bond formation toward aryl phosphonates
Koohgard, Mehdi,Karimitabar, Haniehsadat,Hosseini-Sarvari, Mona
supporting information, p. 17147 - 17151 (2020/12/28)
The combination of black TiO2 nanoparticles (NPs) with a nickel catalyst provides a low-cost, sustainable, and reusable alternative dual catalytic system to a homogeneous counterpart (noble metals). This black TiO2-photoredox/nickel dual catalytic system has efficiently driven C-P bond formation between aryl iodides and diarylphosphine oxides under visible light, providing good to excellent yields as well as tolerating a variety of functional groups. The practical application of this semi-heterogeneous protocol has been highlighted by a sunlight experiment, a gram-scale reaction, and a reusability test.
EUROPIUM COMPLEX
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Paragraph 0379-0381, (2020/11/23)
To provide europium complexes having high photostability. A europium complex expressed with the following formula (A): {wherein, RA and RB are independently a cyclic alkyl group with 3 to 10 carbons, respectively, and RC is a cyclic alkyl group with 3 to 10 carbons or a phenyl group expressed with the following formula (B): (wherein, XA, XB, AC, XD and XE independently represent a hydrogen atom; a fluorine atom; an alkyl group with 1 to 3 carbon(s); an alkyloxy group with 1 to 3 carbon(s); an aryloxy group with 6 to 10 carbons; a fluoroalkyl group with 1 to 3 carbon(s); a fluoroalkyloxy group with 1 to 3 carbon(s); or a phenyl group that may be substituted with a fluorine atom, an alkyl group with 1 to 3 carbon(s), an alkyloxy group with 1 to 3 carbon(s), a fluoroalkyl group with 1 to 3 carbon(s), a fluoroalkyloxy group with 1 to 3 carbon(s), a fluorophenyl group, a hydroxyl group or a cyano group, respectively); RA is a cyclic alkyl group with 3 to 10 carbons; RB and RC are a phenyl group expressed with the formula (B), provided, however, that a case where RA a cyclohexyl group, and, RB and RC are a phenyl group is excluded; or RA, RB and RC independently represent an ortho-substituted phenyl group expressed with the following formula (Ba): (wherein, XE represents a hydrogen atom, an alkyl group with 1 to 3 carbon(s), an alkyloxy group with 1 to 3 carbon(s), a fluoroalkyl group with 1 to 3 carbon(s), a fluoroalkyloxy group with 1 to 3 carbon(s), a naphthyl group that may be substituted with a fluorine atom, a pyridyl group that may be substituted with a fluorine atom, or a phenyl group that is expressed with a formula (C): [wherein, ZA, ZC and ZE independently represent a hydrogen atom, a fluorine atom, an alkyl group with 1 to 3 carbon(s), an alkyloxy group with 1 to 3 carbon(s), a fluoroalkyl group with 1 to 3 carbon(s), a fluoroalkyloxy group with 1 to 3 carbon(s), a phenyl group that may be substituted with a fluorine atom, a hydroxyl group or a cyano group; ZB and ZD independently represent a hydrogen atom or a fluorine atom, respectively], provided, however, that a case where RA, RB and RC are all a phenyl group is excluded), respectively; RD represents a hydrogen atom, a deuterium atom or a fluorine atom; WA and WB independently represent an alkyl group with 1 to 6 carbon(s), a fluoroalkyl group with 1 to 6 carbon(s), a phenyl group, a 2-thienyl group or a 3-thienyl group; and ‘n’ represents an integer of 1 to 3}.
Insertion of Arynes into P-O Bonds: One-Step Simultaneous Construction of C-P and C-O Bonds
Qi, Na,Zhang, Ning,Allu, Srinivasa Rao,Gao, Jiangsheng,Guo, Jian,He, Yun
, p. 6204 - 6207 (2016/12/09)
The insertion of arynes into P-O bonds for the preparation of o-hydroxy-substituted arylphosphine oxides, -phosphinates, and -phosphonates is described. This novel reaction leads to the simultaneous formation of C-P and C-O bonds in one step with good yie
Aryl group - A leaving group in arylphosphine oxides
Stankevi?, Marek,Pisklak, Jolanta,W?odarczyk, Katarzyna
, p. 810 - 824 (2016/01/20)
The treatment of triphenylphosphine oxide with organometallic reagents leads to the substitution of up to three phenyl substituents with the incoming carbon nucleophile. The replacement of the phenyl/aryl group in tertiary diarylalkylphosphine oxides or even aryldialkylphosphine oxides was also observed. Naphthyl-substituted phosphine oxides undergo Michael-type addition at the naphthyl group when treated with organolithium reagent.
Efficient copper(I)-catalyzed coupling of secondary phosphine oxides with aryl halides
Stankevi?, Marek,W?odarczyk, Adam
, p. 73 - 81 (2013/01/15)
A catalytic system has been developed for the efficient synthesis of tertiary arylphosphine oxides by coupling of readily available secondary phosphine oxides with aryl bromides or iodides in the presence of copper(I) iodide as a catalyst and (S)-α-phenylethylamine as a ligand. The system exhibits high activity in the coupling of secondary diaryl-, alkylaryl- and dialkylphosphine oxides.
Memory of axial chirality in aryl radical phosphanylations
Bruch, Achim,Ambrosius, Andrea,Froehlich, Roland,Studer, Armido,Guthrie, David B.,Zhang, Hanmo,Curran, Dennis P.
supporting information; experimental part, p. 11452 - 11454 (2010/10/03)
The rate constant for phosphanylation of an aryl radical with trimethylstannyl diphenylphosphane (Me3SnPPh2) has been measured as kphos ≈ 9 × 108 M-1 s -1. Aryl radicals derived from several axially chiral o-haloanilides are trapped by Me3SnPPh2 with complete retention of axial chirality as shown by oxidation of the phosphanes to give stable, easily analyzed phosphane oxides or sulfides. Double phosphanylations of o,o′-dihaloanilides followed by treatment with H2O2 or S8 in either order give enantiomers of a mixed diphosphane oxide sulfide. Chemodivergent trapping of diastereomers of an N-(cyclohex-2-enyl) anilide anilide is observed. For one isomer, the cyclization precedes the Me3SnPPh2 trapping, while for the other isomer direct trapping with Me3SnPPh2 supersedes the cyclization. The products are chiral triaryl phosphanes, oxides, and sulfides that are potentially interesting ligands in asymmetric catalysis.
