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Construction of a visible light-driven hydrocarboxylation cycle of alkenes by the combined use of Rh(i) and photoredox catalysts

A visible light driven catalytic cycle for hydrocarboxylation of alkenes with CO2 was established using a combination of a Rh(i) complex as a carboxylation catalyst and [Ru(bpy)3]2+ (bpy = 2,2?- bipyridyl) as a photoredox catalyst. Two key steps, the generation of Rh(i) hydride species and nucleophilic addition of pi-benzyl Rh(i) species to CO2, were found to be mediated by light.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Under solvent-free conditions for preparing difluoride […]/1, 2 – ethylene-bis-phosphonium salt method (by machine translation)

The invention relates to a solvent-free conditions for preparing difluoride […]/1, 2 – ethylene-bis-phosphonium salt of the simple method, under the condition without solvent, the organophosphorus and difluoro as ethylating reagent or ethenyl reagent mixing, for – 20 – 150 C stirring for 0.5 – 36h, to be after the reaction is finished, and washing the solid, filtering, the resulting solid oil pump used for drying to obtain the product. The method has the substrate serviceability is good, the operation is simple, easy purification of the product, environment-friendly and the like. By adjusting the reaction temperature and changing the organic phosphine structure, in the same system, can also realize the difluoride […] preparation, two-fluoroacetate […] is a kind of potential fluorine-containing dicing, expected to be used in the synthesis of a plurality of the fluorine compound. (by machine translation)

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Reductive cleavage of the carbon-phosphorus bond with alkali metals. I. Cleavage of functionalised triphenylphosphines; formation of secondary and primary phosphines

The reductive cleavage reaction of functionalised triphenylphosphines 1-34 with Na/NH3 and Li/THF depends strongly on the nature of the functionality and on the reducing agent. No reduction occurs with 11, 24, 30, 31 and 32 in Na/NH3.Compounds 3, 4, 5, 10, 12, 13, 15, 19, 23, 25, 26 and 27 cleave to give the secondary phosphide in high yield with Na/NH3, whereas 2, 7 and 9 give a high yield with Li/THF.Reduction occurs but cleavage is poor with 6, 7, 14, 29 and 34 and Na/NH3, or with 11 and Li/THF.Primary ortho-functionalised phenyl phosphines are obtained by a double cleavage reduction from 2, 5, 12, 25, 26 and 27 with Na/NH3.This unprecedented reaction proceeds via the secondary phosphine, which is formed by protonation of the corresponding phosphide with NH3.It occurs when the aryl group contains a strongly electron-donating substituent.Multiple cleavage of aryl groups with extended ? systems occurs with 7 and 34 when they are made to react with Li/THF.Halogens are cleaved from the phenyl group (16, 17, 18, 28 and 33, with Na/NH3), whereas SCH3 groups are converted to the corresponding mercapto group (20, 21 and 22).Birch reduction (2 and 10) can take place in NH3 but not in the aprotic solvent THF; it occurs only when other reactions are slow.Sodium amide is obtained via reaction of 8 in Na/NH3.Restricted Hartree-Fock calculations were carried out for a number of substituted phenylphosphines.From the correlation between the energies and coefficients of the LUMO (always an aryl ?* orbital) and the experimental cleavage data, it was concluded that there are three requirements for successful cleavage.The LUMO energy should be neither too high (no reduction) nor too low (radical anion too stable) and, further, the coefficient of the LUMO on the carbon attached to phosphorus must be large.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis and Application of Planar Chiral Cyclic (Amino)(ferrocenyl)carbene Ligands Bearing FeCp? Group

New cyclic (amino)(ferrocenyl)carbene (CAFeC) ligands containing the Cp? group have been developed as a modification of their prototype Cp version. The generation of the new carbenes was indirectly confirmed by trapping experiments in which a carbene precursor was reacted with sulfur or [IrCl(cod)]2 in the presence of a base. The electronic properties of the new CAFeCs were evaluated by determining the Tolman electronic parameter (TEP) of the Ir dicarbonyl complex [IrCl(CO)2(CAFeC)] that was synthesized via [IrCl(cod)(CAFeC)]. It was revealed that the donor strengths of the new CAFeCs were very high and comparable to those of cyclic (amino)(alkyl)carbenes (CAACs). The influence of the steric effect on the enantioselectivity by changing Cp to the Cp? group of CAFeCs was confirmed to be significant in an Ir-catalyzed asymmetric transfer hydrogenation of cyclic N-sulfonylimine where CAFeCs were used as chiral ligands.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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1038-95-5, Name is Tri-p-tolylphosphine, molecular formula is C21H21P, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 1038-95-5, Quality Control of: Tri-p-tolylphosphine

Metal-free reduction of tertiary phosphine oxides with Hantzsch ester

The (COCl)2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1038-95-5, Name is Tri-p-tolylphosphine, molecular formula is C21H21P. In a Article£¬once mentioned of 1038-95-5, Computed Properties of C21H21P

Wetting and surface properties of (modified) fluoro-silanised glass

For all of its many useful properties, glass easily gets “dirty”, due to its relatively high surface free energy, thus often necessitating cleaners in operation, such as windscreen wipers. One possible aid is to coat the glass with a hydrophobic layer, thus reducing propensity for contaminant adhesion. We consider the surface properties of two such glasses: a proprietary brand and a laboratory-produced material, being essentially the same, having received similar fluoro-silane coatings. Such fluorinated glasses were subsequently treated using either a solution of sodium in liquid ammonia to create patterns on a millimetric (or larger) scale, or locally electrogenerated radical anions in dimethylformamide (DMF) solution to create smaller patterns. Wetting techniques (sessile drops) have been used to characterise the coated glass both before and after surface reduction. A considerable increase of wettability follows treatment, potentially useful for facilitating assembly of such glasses by adhesives, in specifically limited, treated zones. “Targeted surface treatment” permits the creation of desired motifs of contrasting surface free energy on the glass surface. This technique has been used to study the shape of deformed wetting triple lines. Experimental findings corroborate theoretical predictions for the most part, although some exceptions are discussed.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Olefination of 3-diazopiperidin-2-one

New conditions have been developed for the olefination of diazo compounds catalysed by methyl trioxorhenium. The new system is suitable for unreactive diazo compounds and its utility is demonstrated by the olefination of 3-diazopiperidin-2-one with a range of aromatic, heterocyclic and alkylaldehydes.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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2-HETEROARYL AND 2-HETEROCYCLIC BENZOXAZOLES AS PDE IV INHIBITORS FOR THE TREATMENT OF ASTHMA

Novel compounds which are effective PDE IV inhibitors are disclosed. The present invention is directed to compounds having the general formula I wherein: X is a halogen; Q is -CH2-CH2-, -CH2-, a single or a double bond, or -NR1-; R is a C3-7 monocyclic ring structure containing at least one carbon atom and comprising one or more chalcogen atoms selected from the group consisting of nitrogen, sulfur and oxygen, wherein the monocyclic ring is unsaturated, partially unsaturated or saturated, and is optionally substituted with alkyl, cycloalkyl, alkoxy, cycloalkoxy, hydroxy or halogen; or is a bicyclic structure, comprised of a phenyl ring fused to a monocyclic ring structure as defined above, or comprised of two fused monocyclic ring structures, each ring containing at least one carbon atom and comprising one or more chalcogen atoms selected from the group consisting of nitrogen, sulfur and oxygen, wherein the monocyclic ring is unsaturated, partially unsaturated or saturated, and is optionally substituted with alkyl, cycloalkyl, alkoxy, cycloalkoxy, hydroxy or halogen. R2 is a phenyl group or a C3-7 monocyclic ring structure containing at least one carbon atom and comprising one or more chalcogen atoms selected from the group consisting of nitrogen, sulfur and oxygen, wherein the monocyclic ring may be unsaturated, partially unsaturated or saturated, and is optionally substituted with alkyl, cycloalkyl, alkoxy, cycloalkoxy, hydroxy or halogen

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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METHOD

The invention provides mitochondria-targeted chemiluminescent agents and their use in methods of photodynamic therapy (PDT). In particular, the invention provides compounds of general formula (I), and their pharmaceutically acceptable salts: (I) in which A represents a chemiluminescent moiety; each L, which may be the same or different, is either a direct bond or a linker; each B, which may be the same or different, represents a mitotropic moiety; n is an integer from 1 to 3, preferably 1; and x is an integer from 1 to 3, preferably 1. Such compounds find particular use in the treatment of deeply- sited tumours, e.g. glioblastoma multiforme (GBM), when used in combination with a photosensitizer or photosensitizer precursor.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis of luminescent alkynyl gold metalaligands containing 2,2?-bipyridine-5-yl and 2,2?:6?,2?-terpyridine-4-yl donor groups

[AuCl(SMe2)] reacts with HC?CR (R = bpyl = 2,2?-bipyridine-5-yl (1), phtpyl = phenyl-4-(2,2?: 6?,2?-terpyridine-4-yl) (2)) and NEt3 (1:1:3) to afford the polymers [Au(C?CR)]n (R = bpyl (3), phtpyl (4)). The new alkyne HC?Cphccbpyl (5, phccbpyl = 4-C6H4C? CbPyl) has been prepared by Sonogashira coupling of 4-Me3SiC? CC6H4I and 1 followed by desilylation of the resulting alkyne 4-Me3SiC?Cphccbpyl. The alkynyl Au(I) complexes [Au(C?CR)L] (R = bpyl, L = PPh3 (6), PTol3 (7, Tol = 4-MeC6H4), PEt3 (8); R = phtpyl, L = XyNC (9), PPh3 (10); R = phccbpyl, L = PPh3 (11)) have been prepared by reacting: (1) 3 or 4 with L or (2) the corresponding alkyne 1,2, or 5 with [Au(acac)(PPh3)] (acac = acetylacetonato). The reaction of 3 or 4 with diphosphines gives [(Au(C?CR) }2(muPh 2P(CH2)XPPh2)] (R = bpyl, x = 1 (12), 2 (13), 4 (14), 10 (15); R = phtpyl, x = 10 (16)). ESI mass spectrometric studies show that complexes 12-14 are in equilibrium with the salts [Au 3(C?Cbpyl)2(muPh2P(CH2) xPPh2)2][Au(C?Cbpyl)2], although only when x = 1 (17) was a significant concentration of the salt detected by NMR spectroscopy and isolated. The anionic complexes PPN[Au(C?CR)2] (R = bpyl (18), phtpyl (19), or phccbpyl (20)) have been prepared by reaction of the corresponding alkynes with PPN[Au(acac)2]. Complexes 6, 10, 13, 14, 17, and 18 have been characterized by single-crystal X-ray diffraction studies. The alkynyl complexes are luminescent at room temperature, displaying dual emissions.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate