- Ultrashort Hδ+?Hδ?intermolecular distance in a supramolecular system in the solid state
-
Herein we report experimental evidence for the shortest intermolecular distance reported for two electronically-different hydrogen atoms in the solid state. The Hδ+?Hδ?non-covalent interaction was studied using theoretical calculatio
- Frontera, Antonio,García-Márquez, Alfonso,Gramage-Doria, Rafael,Roisnel, Thierry
-
p. 7112 - 7115
(2021/07/28)
-
- Phosphite sodium salt modified amphipathic phosphorus-containing crown macromolecule nano micelle and preparation and application thereof
-
The invention relates to a phosphite sodium salt modified amphipathic phosphorus-containing crown macromolecule nano micelle and a preparation method and application thereof. The preparation method is simple, the controllability of the reaction process is high, and the operation is easy. Compared with the reported polyamide - amine type crown macromolecule nano-micelle, the nano material has higher encapsulation efficiency, loading rate and better anti-inflammatory effect, can effectively improve the treatment effect of the hydrophobic drug, and has good application prospects.
- -
-
Paragraph 0086; 0093
(2021/08/25)
-
- Phosphine boranes as less hydrophobic building blocks than alkanes and silanes: Structure-property relationship and estrogen-receptor-modulating potency of 4-phosphinophenol derivatives
-
Increasing structural options in medicinal chemistry is important for the development of novel and distinctive drug candidates. In this study, we focused on phosphorus-containing functionalities. We designed and synthesized a series of phosphinophenol der
- Fujii, Shinya,Hashimoto, Yuichi,Matsumoto, Yuichiro,Saito, Hiroki
-
-
- Shuttling Catalyst: Facilitating C?C Bond Formation via Cross-Couplings with a Thermoresponsive Polymeric Ligand
-
A poly(ethylene glycol) (PEG) linked ortho-MeO-phenyldicyclohexylphosphine (MeO-WePhos) ligand has been synthesized to promote Pd-catalyzed carbon-carbon bond formation by cross-couplings including Sonogashira, Heck, Hiyama and Stille reactions, providing corresponding (hetero)aryl substituted alkynes, alkenes and bi(hetero)aryls in good to excellent isolated yields with low Pd loadings. Facilitated by the lower critical solution temperature behaviour of the polymeric monophosphine ligand, the metal-complex could rapidly shuttle between organic and water phases as regulated by temperature, enabling highly efficient catalyst recycling via a simple phase separation. The chemical structure of ligand was determined by matrix-assisted laser desorption/ionization-time of flight mass spectrometry, nuclear magnetic resonance spectrometry and size-exclusion chromatography measurements. Notably, as demonstrated by the inductively coupled plasma-atomic emission spectrometry measurement, 98% Pd was kept in the water phase after 6 cycles of catalyst recycling experiments. Given the profound impact of transition-metal-catalyzed covalent bond formation and the increasing demand of sustainable chemistry, this work provides an alternative method to conduct cross-couplings with a polymeric shuttling catalyst.
- Wang, Erfei,Zhang, Jiawei,Zhong, Zhuoran,Chen, Kaixuan,Chen, Mao
-
p. 419 - 423
(2020/01/08)
-
- Preparation method of amphiphilic PN = PS type phosphorus-containing crown macromolecular nano-micelle and application of crown macromolecular nano-micelle as drug carrier
-
The invention relates to a preparation method of amphipathic PN = PS type phosphorus-containing crown macromolecule nano-micelle and application of the crown macromolecular nano-micelle as a drug carrier. The obtained amphipathic phosphorus-containing crown macromolecule can be self-assembled into the nano-micelle in water, and a hydrophobic drug can be embedded into a hydrophobic cavity in the nano-micelle to form a stable compound. The method disclosed by the invention is simple, high in reaction controllability, easy in operation and separation, low in cost, uniform in final product molecular weight and commercialized in raw material source, and has a good development prospect.
- -
-
Paragraph 0076; 0083
(2020/11/10)
-
- Readily Available Immobilized Pd Catalysts for Suzuki-Miyaura Coupling under Continuous-flow Conditions
-
Highly efficient immobilized catalysts for continuous-flow cross-coupling reactions that show better productivity than those for the corresponding batch reactions are increasingly in demand. For practical use, such catalysts should have highly catalytic activity and high leaching resistance. To find catalysts suitable for continuous-flow conditions, we have developed a consistent method for evaluating the catalytic performance of commercially available immobilized Pd catalysts. Monitoring of the change in turnover frequency over time under excess substrate loading conditions revealed the limitation of these catalysts. On the basis of the evaluation results, we have successfully developed a new immobilized Pd catalyst that exhibited highly efficient and robust catalytic performance.
- Ichitsuka, Tomohiro,Suzuki, Naoto,Sairenji, Masaki,Koumura, Nagatoshi,Onozawa, Shun-ya,Sato, Kazuhiko,Kobayashi, Shū
-
p. 2427 - 2431
(2019/04/27)
-
- PHOSPHONIUM COMPOUND AND PRODUCTION METHOD THEREFOR
-
The present invention provides a phosphonium compound of formula (II). Also provided is a method for producing a quaternary phosphonium compound labeled with a positron emitting radionuclide, the method comprising the step of reacting an electrophile of f
- -
-
Paragraph 0156-0159
(2018/02/28)
-
- A general strategy to add diversity to ruthenium arene complexes with bioactive organic compounds: Via a coordinated (4-hydroxyphenyl)diphenylphosphine ligand
-
Esterification of (4-hydroxyphenyl)diphenylphosphine, coordinated to the [Ru(η6-p-cymene)Cl2] fragment, allows a series of bioactive carboxylic acids to be introduced directly into the organometallic molecule. Evaluation of the compounds on human ovarian cancer cells reveals synergistic enhancements in their antiproliferative activity relative to their bioactive organic and organometallic precursors.
- Biancalana, Lorenzo,Batchelor, Lucinda K.,De Palo, Alice,Zacchini, Stefano,Pampaloni, Guido,Dyson, Paul J.,Marchetti, Fabio
-
supporting information
p. 12001 - 12004
(2017/09/25)
-
- Early-Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity
-
OH functionalized triarylphosphines were used to assemble zirconocene-based metalloligands with phosphine donor sites in varying positions. These complexes were subsequently treated with different gold precursors to obtain early-late heterometallic compou
- Bestgen, Sebastian,Schoo, Christoph,Zovko, Christina,K?ppe, Ralf,Kelly, Rory P.,Lebedkin, Sergei,Kappes, Manfred M.,Roesky, Peter W.
-
p. 7115 - 7126
(2016/05/19)
-
- PHOSPHONIUM COMPOUND OR INTERMOLECULAR SALT THEREOF, AND METHOD OF PRODUCING THE SAME
-
PROBLEM TO BE SOLVED: To provide a compound useful as a curing accelerator of an epoxy resin composition and a method of producing the same. SOLUTION: This invention provides a phosphonium compound represented by general formula (I-1) or intermolecular sa
- -
-
Page/Page column 0069
(2016/10/08)
-
- Recycling Pd colloidal catalysts using polymeric phosphine ligands and polyethylene as a solvent
-
Polyisobutylene (PIB)-bound azo dyes were prepared from aryl amine terminated polyisobutylene oligomers and used to form palladacycle precatalysts that can be used for catalytic carbon-carbon cross coupling reactions. The catalysts so formed were recyclable using thermomorphic heptane-DMF solutions that are monophasic at 80 °C and biphasic at room temperature. Under these conditions, the Pd catalyst can be recycled but some Pd leaches into the product solution. Using a low melting polyethylene oligomer as a solvent in place of the volatile heptane solvent reduces this leaching by roughly an order of magnitude. Further modification that involves using a second polyisobutylene (PIB)-bound phosphine ligand both increases the activity of the colloidal Pd catalyst and decreases the total Pd leaching by almost two orders of magnitude with 99.88% of the Pd being recovered. In this case, the Pd content in the solution of the product was ca. 0.3 ppm. These two modifications together lead to a much more sustainable strategy for the use of Pd colloidal catalysts in catalytic cross coupling chemistry.
- Priyadarshani, Nilusha,Suriboot, Jakkrit,Bergbreiter, David E.
-
p. 1361 - 1367
(2013/06/27)
-
- Enhanced catalytic activity in suzuki-miyaura couplings by shell crosslinked pd nanoparticles from alkene-terminated phosphine dendron-stabilized Pd nanoparticles
-
New alkene-terminated phosphine dendron-protected palladium nanoparticles (NPs) have been synthesized, and the olefin metathesis polymerization of their Pd NPs led to shell crosslinked Pd NPs without aggregation of the Pd NPs. The introduction of crosslinking at the surface of the protective ligand enhanced the catalytic activity of the Pd NPs for SuzukiMiyaura couplings.
- Shiomi, Toshiaki,Nakahodo, Tsukasa,Fujihara, Hisashi
-
p. 1700 - 1702
(2013/02/23)
-
- Novel phosphite palladium complexes and their application in C-P cross-coupling reactions
-
A mono- and a 1,3-bis-phosphite arene ligand based on 2,2′-biphenol have been synthesized in order to study the synthesis of the corresponding palladium(II) complexes starting from different Pd precursors. Novel bis-phosphite palladium complex 1 [PdCl2(L)2] (L = dibenzo[d,f][1,3,2]dioxaphosphepin, 6-phenoxy), C,P-chelate bonded monophosphite palladium complex 2 [Pd(κ2-L)(μ-Cl)]2, and PCP-pincer palladium complex 3 have been prepared from these ligands in promising to excellent yields (50-95%). Additionally, complexes 1 and 3 have been characterized by X-ray crystal structure determinations. The application of 2,6-bis-phosphite pincer palladium(II) complex 3 in C-P cross-coupling between diphenylphosphine-borane and a wide range of various aryl iodides under very mild conditions is reported. Kinetic investigations indicate that 3 merely acts as a pre-catalyst and that Pd nanoparticles are the actual catalytically active species.
- Li, Jie,Lutz, Martin,Spek, Anthony L.,Van Klink, Gerard P.M.,Van Koten, Gerard,Klein Gebbink, Robertus J.M.
-
experimental part
p. 2618 - 2628
(2010/11/21)
-
- Variable-temperature NMR studies of soluble polymer-supported phosphine-silver complexes
-
(Chemical Equation Presented) The use of polymers as supports for organometallic catalysts has received wide attention. However, catalyst reactivity is sometimes altered as a consequence of catalyst immobilization by a polymeric ligand and such altered reactivity can complicate such supported catalysts' use. The results in this study show that heptane phase selectively soluble polyisobutylene (PIB)-bound phosphine ligands have essentially identical kinetic behavior when compared to electronically similar isobutyldiphenylphosphine analogues in phosphine coordination and exchange in silver(I) halide complexes. These studies used variable-temperature 31P NMR spectroscopy to probe the silver-phosphine exchange processes for both AgI and AgCl complexes of these polymeric and low molecular weight phosphine ligands. The results show that the dynamic behavior of the PIB- and isobutyldiphenylphosphine-AgX complexes is nearly identical based on line-shape analysis of these 31P NMR spectra as a function of temperature. Similar studies of more polar poly(ethylene glycol)triarylphosphine-bound AgX complexes and electronically analogous low molecular weight AgX complexes have similar behavior in variable-temperature 31P NMR spectroscopy.
- Bergbreiter, David E.,Yang, Yun-Chin
-
scheme or table
p. 873 - 878
(2010/04/30)
-
- Low molecular weight MPEG-assisted organic synthesis
-
A toolkit of low molecular weight MPEG-supported coupling agents ( MIIDQ, MEDCI), reagents for the Mitsunobu reaction ( MDEAD, MTPP), an alternative to diazomethane, and scavengers can be used in the solution-phase synthesis of amides, esters and ureas and are easily removed after use by solid-phase extraction (MSPE) using normal silica.
- Figlus, Marek,Tarruella, Albert C.,Messer, Anastasia,Sollis, Steven L.,Hartley, Richard C.
-
supporting information; experimental part
p. 4405 - 4407
(2010/09/15)
-
- Nanotube composites consisting of metal nanoparticles and polythiophene from electropolymerization of terthiophene-functionalized metal (Au, Pd) nanoparticles
-
We have developed a new method for the fabrication of metal nanoparticle/polythiophene nanotube composites, i.e., the template-based electrochemical polymerization of terthiophene-linked oligoethyleneoxy-thiol (1) and -phosphine (2)-stabilized gold and pa
- Umeda, Ryuhei,Awaji, Hiroshi,Nakahodo, Tsukasa,Fujihara, Hisashi
-
p. 3240 - 3241
(2008/09/20)
-
- Homogeneous catalysts supported on soluble polymers: Biphasic Sonogashira coupling of aryl halides and acetylenes using MeOPEG-bound phosphine - Palladium catalysts for efficient catalyst recycling
-
The Sonogashira coupling of various aryl bromides and iodides with different acetylenes was studied under biphasic conditions with soluble, polymer-modified catalysts to allow the efficient recycling of the homogeneous catalyst. For this purpose, several
- Koellhofer, Axel,Plenio, Herbert
-
p. 1416 - 1425
(2007/10/03)
-
- Exploiting poly(ethylene glycol) as a matrix for liquid-phase organic synthesis
-
Soluble polymer-supported chemistry is a technology that allows the blending of the benefits of polymer-supported synthesis and solution-phase chemistry. Herein, we describe our recent efforts in this area targeted at exploring the scope of poly(ethylene glycol) (PEG) as the matrix. Specifically we describe the use of PEG as a support for triphenyl phosphine and for the Stille reaction.
- Sieber, Frank,Wentworth Jr., Paul,Janda, Kim D.
-
p. 1018 - 1032
(2007/10/03)
-
- Development and Application of a Poly(ethylene glycol)-Supported Triarylphosphine Reagent: Expanding the Sphere of Liquid-Phase Organic Synthesis
-
Continuing studies into the utility of poly(ethylene glycol) (PEG)-supported triarylphosphines as functional polymer reagents in liquid-phase organic synthesis (LPOS) are being pursued. This report describes the synthesis and NMR characterization of an aryl-alkyl ether-linked PEG-triarylphosphine derivative (2) and its subsequent application in LPOS. The utility of 2 as a mild stoichiometric reagent for ozonide reduction has been demonstrated, and a direct comparison between 2, a Merrifield resin-bound triarylphosphine derivative, and a solution-phase triphenylphosphine reagent revealed that the highest observed yields occur under liquid-phase conditions. Transformation of phosphine 2 into a phosphonium salt (3) then allowed the inherent aqueous solubility of PEG-functionalized moieties to be exploited by enabling a Wittig reaction, between a range of aldehydes and 3, to occur under mildly basic aqueous conditions. This led to the generation of substituted stilbenes in good to excellent yields. Finally, regeneration of 2 was achieved by reduction of the PEG-supported triphenylphosphine oxide byproduct 4 with alane (100% conversion, 75% yield). This combination of reaction, recovery, and regeneration expands the utility of PEG-supported triarylphosphine reagents across the spectra of both organic chemistry and solution-phase combinatorial strategies.
- Sieber, Frank,Wentworth Jr., Paul,Toker, Jonathan D.,Wentworth, Anita D.,Metz, William A.,Reed, Neal N.,Janda, Kim D.
-
p. 5188 - 5192
(2007/10/03)
-
- Water soluble phosphines VIII. Palladium-catalyzed P-C cross coupling reactions between primary or secondary phosphines and functional aryliodides - A novel synthetic route to water soluble phosphines
-
Tertiary phosphines Ph2P-Ar and PhP(Ar)2 containing mono-and disubstituted aromatic ring systems Ar (Ar = C6H4-X and C6H3-XY; X, Y = Me, OH, NH2, COOH, COOMe and SO3Na) are accessible in good yields by Pd(0)-catalyzed cross coupling reactions between diphenylphosphine or phenylphosphine and substituted aryliodides I-C6H4-X or I-C6H3-XY in organic solvents (dimethylacetamide, acetonitrile, methanol) using organic amines or potassium and sodium acetate as bases. If the primary phosphine is employed in the appropriate stoichiometric ratio, functionalized secondary phosphines, e.g. Ph(H)P-C6H4-p-SO3Na, may be obtained selectively.
- Herd, Oliver,Hessler, Antonella,Hingst, Martin,Tepper, Michael,Stelzer, Othmar
-
-