79932-99-3Relevant academic research and scientific papers
Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
Arockiam, Percia Beatrice,Lennert, Ulrich,Graf, Christina,Rothfelder, Robin,Scott, Daniel J.,Fischer, Tillmann G.,Zeitler, Kirsten,Wolf, Robert
supporting information, p. 16374 - 16382 (2020/11/03)
Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
, (2018/07/31)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine
Xu, Zhaotao,Wang, Pingping,Chen, Qiurong,Cai, Mingzhong
, p. 50 - 58 (2018/04/23)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in DMAc at 130 °C in the presence of 1.0 mol% of MCM-41-supported tridentate nitrogen palladium(0) complex [MCM-41-3N-Pd(0)] with KOAc as base, yielding a variety of unsymmetrical triarylphosphines in good to excellent yields. The turnover frequency (TOF) of the catalyst can reach 30.67 h?1. This new heterogeneous palladium(0) catalyst could easily be prepared by a simple procedure from commercially readily available reagents, and exhibited the same catalytic activity as homogeneous Pd(OAc)2 or Pd(PPh3)4, and could be recovered by filtration of the reaction solution and recycled at least seven times without significant loss of catalytic activity.
O,o-Difluorination of aromatic azide yields a fast-response fluorescent probe for H2S detection and for improved bioorthogonal reactions
Zhang, Jie,Gao, Yasi,Kang, Xueying,Zhu, Zhentao,Wang, Zhiqian,Xi, Zhen,Yi, Long
, p. 4212 - 4217 (2017/07/10)
The development of efficient bioorthogonal reactions for sensing of endogenous biomolecules and for bioconjugation should be of paramount importance in the field of chemical biology. In this work, the o,o′-difluorinated aromatic azide was firstly employed to develop a new fast-response fluorescent probe 1 for H2S detection and for bioorthogonal reactions. Compared with non- and mono-fluorinated probes, 1 showed faster reaction toward H2S, the third gasotransmitter, in buffer (pH 7.4), implying that the reaction rate could be enhanced by the dual-fluorine groups. Furthermore, such enhanced reaction rates of 1 were also observed in the Staudinger reaction and strain-promoted azide-alkyne cycloaddition (SPAAC) based on the comparison studies of the non-fluorinated probe. Our results firstly highlight that the o,o′-difluorinated aromatic azide group should be useful for fast bioorthogonal reactions and H2S detection.
Perfluoroaryl Azide Staudinger Reaction: A Fast and Bioorthogonal Reaction
Sundhoro, Madanodaya,Jeon, Seaho,Park, Jaehyeung,Ramstr?m, Olof,Yan, Mingdi
supporting information, p. 12117 - 12121 (2017/09/07)
We report a fast Staudinger reaction between perfluoroaryl azides (PFAAs) and aryl phosphines, which occurs readily under ambient conditions. A rate constant as high as 18 m?1 s?1 was obtained between methyl 4-azido-2,3,5,6-tetrafluorobenzoate and methyl 2-(diphenylphosphanyl)benzoate in CD3CN/D2O. Furthermore, the iminophosphorane product was stable toward hydrolysis and aza-phosphonium ylide reactions. This PFAA Staudinger reaction proved to be an excellent bioothorgonal reaction. PFAA-derivatized mannosamine and galactosamine were successfully transformed into cell-surface glycans and efficiently labeled with phosphine-derivatized fluorophore-conjugated bovine serum albumin.
2-(diphenylphosphino)benzoic acid and synthetic method thereof
-
Paragraph 0040-0044; 0047-0050; 0053-0056; 0059-0062, (2017/07/25)
The invention relates to a pesticide intermediate and a synthetic method thereof, and in particular relates to 2-(diphenylphosphino)benzoic acid and a synthetic method thereof, belonging to the technical field of chemical synthesis. The synthetic method of the 2-(diphenylphosphino)benzoic acid comprises the following steps: A, metallic sodium cracks chlorodiphenylphosphine in a refluxing organic solvent to generate sodium diphenylphosphine; B, methyl 2-chlorobenzoate is added to the sodium diphenylphosphine and reacts to generate diphenylphosphine benzoate; and C, the diphenylphosphine benzoate refluxes and reacts with 10% sodium hydroxide first to generate diphenylphosphine sodium benzoate, and then the diphenylphosphine sodium benzoate is hydrolyzed to obtain 2-(diphenylphosphino)benzoic acid. The synthetic method has the advantages of cheap and easily available raw materials, greenness, environment friendliness and no use of expensive reagents such as metallic lithium, so that the synthetic method has simple reaction conditions, few impurities, high yield, high quality and high purity of the prepared 2-(diphenylphosphino)benzoic acid, and high recovery rate of other reagents, for example, the recovery rate of organic solvents is greater than 93%, and the synthetic method can be widely used for synthesizing high-quality intermediates of pesticide.
A phosphine oxygen radical hydrogen anthracene two - three fragrant amine compound and use thereof
-
Paragraph 0069; 0077, (2016/10/09)
The invention relates to a bipolar organic material with a phosphorus oxygen functional group and a triarylated amine functional group. The general formula of the compound is shown in the description (Pn). The bipolar compound provided by the invention can be used as a main material of a triplet luminescent dye or a carrier transport material, has a triplet-state energy level, has the characteristics of high carrier transport capability and high stability, and can also transport an electron and a hole, so that the charge transfer balance of a luminance layer is guaranteed effectively, the brightness and the efficiency of an organic electroluminescence device are correspondingly improved, the service life of the organic electroluminescence device is prolonged, and the defects of low efficiency and short service life of the device at large current are overcome.
A reductant-resistant and metal-free fluorescent probe for nitroxyl applicable to living cells
Kawai, Kodai,Ieda, Naoya,Aizawa, Kazuyuki,Suzuki, Takayoshi,Miyata, Naoki,Nakagawa, Hidehiko
supporting information, p. 12690 - 12696 (2013/09/23)
Nitroxyl (HNO) is a one-electron reduced and protonated derivative of nitric oxide (NO) and has characteristic biological and pharmacological effects distinct from those of NO. However, studies of its biosynthesis and activities are restricted by the lack of versatile HNO detection methods applicable to living cells. Here, we report the first metal-free and reductant-resistant HNO imaging probe available for use in living cells, P-Rhod. It consists of a rhodol derivative moiety as the fluorophore, linked via an ester moiety to a diphenylphosphinobenzoyl group, which forms an aza-ylide upon reaction with HNO. Intramolecular attack of the aza-ylide on the ester carbonyl group releases a fluorescent rhodol derivative. P-Rhod showed high selectivity for HNO in the presence of various biologically relevant reductants, such as glutathione and ascorbate, in comparison with previous HNO probes. We show that P-Rhod can detect not only HNO enzymatically generated in the horseradish peroxidase-hydroxylamine system in vitro but also intracellular HNO release from Angeli's salt in living cells. These results suggest that P-Rhod is suitable for detection of HNO in living cells.
Discovery of a robust and efficient homogeneous silver(I) catalyst for the cycloaddition of azides onto terminal alkynes
McNulty, James,Keskar, Kunal
, p. 5462 - 5470 (2012/10/30)
A highly efficient, chemically stable, and well-defined homogeneous silver(I) catalyst is reported for the cycloaddition of azides onto terminal alkynes (Ag-AAC reaction). The Ag-AAC reaction occurs at room temperature or with heating to deliver exclusive
Fluoride catalyzed P-aryl-coupling - A mild approach to functionalized arylphosphines
Reis, Andreas,Dehe, Daniel,Farsadpour, Saeid,Munstein, Isabel,Sun,Thiel, Werner R.
supporting information; experimental part, p. 2488 - 2495 (2012/01/04)
Functionalized triaryl- and diarylalkylphosphines are accessible in high yields following a mild fluoride catalyzed phosphorous-carbon coupling protocol starting from fluoroarenes and silylated phosphines. The reaction requires a minimum of solvent and ca
