7333-67-7Relevant articles and documents
Enabling Mitochondrial Uptake of Lipophilic Dications Using Methylated Triphenylphosphonium Moieties
Ong, How Chee,Hu, Zhang,Coimbra, Jo?o T. S.,Ramos, Maria J.,Kon, Oi Lian,Xing, Bengang,Yeow, Edwin K. L.,Fernandes, Pedro A.,García, Felipe
, p. 8293 - 8299 (2019)
Triphenylphosphonium (TPP+) species comprising multiple charges, i.e., bis-TPP+, are predicted to be superior mitochondrial-targeting vectors and are expected to have mitochondrial accumulations 1000-fold greater than TPP+, the current "gold standard". However, bis-TPP+ vectors linked by short hydrocarbon chains (n + moieties (T*PP+), we successfully enabled the accumulation of bis-TPP+ with a short linker chain in isolated mitochondria, as measured by high performance liquid chromatography. These experimental results are further supported by molecular dynamics and ab initio calculations, revealing the strong correlations between mitochondria uptake and molecular volume, surface area, and chemical hardness. Most notably, the molecular volume has been shown to be a strong predictor of accumulation for both mono- and bis-TPP+ salts. Our study underscores the potential of T*PP+ moieties as alternative mitochondrial vectors to overcome low permeation into the mitochondria.
Synthesis, crystal structure, Hirshfeld surface analysis, DFT calculations and characterization of 1,3-propanediylbis(triphenylphosphonium) monotribromide as brominating agent of double bonds and phenolic rings
Gholizadeh, Mostafa,Nokhbeh, Seyed Reza,Salimi, Alireza,Sparkes, Hazel A.
, (2020)
This paper presents synthesis and structural characterization of new members of phosphorus-based organic bromides. 1,3-Propanediylbis(triphenylphosphonium) dibromide I and 1,3-propanediylbis(triphenylphosphonium) monotribromide II, as a new brominating agent for double bonds and phenolic rings, were synthesized. 1H NMR, 13C NMR, 31P NMR, FT-IR, single crystal X-ray diffraction crystallography, differential scanning calorimetry, thermogravimetric analysis and differential thermal analysis were used to characterize these salts. Thermal and physicochemical stability, simple working up, non-toxicity in comparison to liquid bromine and high yield are some of the advantages of these salts. These salts have good solubility in organic solvents, such as methanol, ethanol, acetone, dichloromethane and THF. Crystallographic data showed that compound I crystallized in the monoclinic crystal system, in P21 space group and compound II crystallized in the monoclinic crystal system, in P21/c space group and one of the bromide ions was replaced by tribromide ion in II. The crystal packing structures of title compounds were stabilized by various intermolecular interactions, especially of the type C-H???π contacts. The molecular Hirshfeld surface analysis and 2D fingerprint analysis revealed that the C???H (30.4% for the compound I and 28.3% for compound II) contact, which was related to C-H???π interactions, had the major contribution in the crystal architectures. To get more insight about molecular structures of titled compounds, DFT calculations were performed (energy, structural optimization and natural bond orbital analysis). Bromination of double bonds and phenolic rings was carried out to prove the ability of the tribromide salt to bromine such organic substrates.
Synthesis, crystal and structural characterization, Hirshfeld surface analysis and DFT calculations of three symmetrical and asymmetrical phosphonium salts
Delaram, Behnaz,Gholizadeh, Mostafa,Makari, Faezeh,Nokhbeh, Seyed Reza,Salimi, Alireza
, (2021/07/01)
Three stable phosphonium salts of 1,4-butanediylebis(triphenylphosphonium) dibromide I, butane-4?bromo-1-(triphenylphosphonium) bromide II and 1,3-propanediylbis(triphenylphosphonium) tetrahydroborate III were synthesized and structurally characterized. Single crystal X-ray diffraction analysis, spectroscopic methods and thermal analysis methods were used for the characterization of titled compounds. Crystallographic data showed that compound I crystallized in the triclinic crystal system with Pī space group and compound II crystallized in the monoclinic crystal system with P21/c space group. The crystal packing structures of I and II were stabilized by various intermolecular interactions, especially of C–H···π contacts. The molecular Hirshfeld surface analysis and 2D fingerprint revealed that the C···H contacts have 24.3% and 18.4% contributions in the crystal packings of compounds I and II, respectively. In addition, the H···Br (28.5%) contact has a considerable contribution to the crystal architecture of compound II. Theoretical studies were performed by DFT method to investigate the structural properties of the titled compounds. The isotopic ratio of boron in tetrahydroborate anion of compound III calculated by 1H NMR spectroscopy. The isotopic ratio for 10B/11B was 19.099 / 80.900%. Reduction of some carbonyl compounds to corresponding alcohols was performed by compound III and the optimum conditions were determined.
Evaluation of bifunctional chiral phosphine oxide catalysts for the asymmetric hydrosilylation of ketimines
Warner, Christopher J.A.,Berry, Sian S.,Jones, Simon
, (2019/11/11)
A series of bifunctional phosphine oxides have been prepared and evaluated as catalysts for the trichlorosilane mediated asymmetric hydrosilylation of ketimines. bis-Phosphine oxides, hydroxy-phosphine oxides, and biaryl phosphine oxides all demonstrated good catalytic activity, but poor to moderate enantioselectivity. A bis-P-chiral phosphine oxide displayed the highest enantioselectivity of 60%.
ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis
Moore, Peter W.,Read, Christopher D. G.,Bernhardt, Paul V.,Williams, Craig M.
supporting information, p. 4556 - 4561 (2018/03/13)
The Ley–Griffith tetra-n-propylammonium perruthenate (TPAP) catalyst has been widely deployed by the synthesis community, mainly for the oxidation of alcohols to aldehydes and ketones, but also for a variety of other synthetic transformations (e.g. diol cleavage, isomerizations, imine formation and heterocyclic synthesis). Such popularity has been forged on broad reaction scope, functional group tolerance, mild conditions, and commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) that mirror the reactivity of TPAP, but avoid storage decomposition issues.
Synthesis of ethyl 5Z,9Z,12Z-octadecatrienoate (ethyl pinolenate) and methyl 12Z,15Z-octadecadienoate
Kaltia, Seppo,Matikainen, Jorma,Ala-Peijari, Maija,Hase, Tapio
, p. 561 - 565 (2008/09/20)
Pinolenic acid (5Z,9Z,12Z-octadecatrienoic acid, 1a), one of the most abundant trienoic fatty acids in nature, is very difficult to obtain in quantity in a pure state from the highly complex mixture of unsaturated tall oil fatty acids. For this reason its chemistry has been little studied when compared to linolenic or linoleic acids. A simple synthesis of esters of 1a and of 12Z,15Z-octadecadienoic acid 3 using the one pot double Wittig procedure is described here. The products of double Wittig reactions were purified by argentation chromatography, and their structural purity was established by 1H-, 13C-NMR and 2D-NMR spectroscopies.
Unsymmetrical double Wittig olefination on the syntheses of insect pheromones. Part 1: Synthesis of 5,9-dimethylpentadecane, the sexual pheromone of Leucoptera coffeella
Zarbin, Paulo H. G.,Princival, Jefferson L.,De Lima, Eraldo R.,Dos Santos, Alcindo A.,Ambrogio, Bianca G.,De Oliveira, Alfredo R. M.
, p. 239 - 241 (2007/10/03)
An expeditious three-step synthesis of a mixture of stereoisomers of 5,9-dimethylpentadecane 1, the sexual pheromone of the coffee leaf miner Leucoptera coffeella, is described. The route employs an unsymmetrical double Wittig olefination to build the carbon skeleton of the molecule, as the key reaction. The bis-phosphonium salt 3, derived from 1,3-dibromopropane 2, reacted 'one-pot' with the ketones 2-octanone and 2-hexanone, affording the asymmetric diene 4. This was readily hydrogenated over Pd/C, furnishing pheromone 1 in 54% overall yield. Synthetic 1 showed high biological activity when tested in field experiments.
Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins
-
, (2008/06/13)
The present invention provides a method of preparing a phosphonium salt of the formula [R1R2R3P—CR4R5R6]X, comprising ball-milling a phosphine of the formula R1R2R3P with a compound of the formula XCR4R5R6; a method of preparing a phosphorus ylide of the formula R1R2R3P═CR4R5, comprising ball-milling a phosphonium salt of the formula [R1R2R3P—HCR4R5]X in the presence of a base; and a method of preparing an olefin of the formula R4R5C═CR7H or R4R5C═CR7R8, comprising ball-milling a phosphorus ylide of the formula R1R2R3P═CR4R5 with a compound of the formula R7C(O)H or R7C(O)R8. The inventive method produces phosphonium salts and phosphorus ylides by mechanical processing solid reagents under solvent-free conditions. The advantages of the present invention over conventional solution methods, include: (1) extremely high selectivity; (2) high yields; (3) low processing temperatures; (4) simple and scalable reactions using commercially available equipment; and (5) the complete elimination of solvents from the reaction.
Solvent-free mechanochemical synthesis of phosphonium salts
Balema, Viktor P.,Wiench, Jerzy W.,Pruski, Marek,Pecharsky, Vitalij K.
, p. 724 - 725 (2007/10/03)
Phosphonium salts have been prepared during high-energy ball-milling of triphenylphosphine with solid organic bromides; the reactions occur at ambient conditions without a solvent; in the case of 2-bromo-2-phenylacetophenone the reaction in a solution usually produces a mixture containing both the C-phosphorylated and O-phosphorylated compounds, while the solvent-free mechanically induced transformation results in the thermodynamically favorable C-phosphorylated product; the occurrence of the observed transformations during mechanical processing of solid reactants is confirmed by the solid-state 31P NMR spectroscopy and X-ray powder diffraction.
Understanding the structural properties of a homologous series of bis-diphenylphosphine oxides
Calcagno, Patrizia,Kariuki, Benson M.,Kitchin, Simon J.,Robinson, James M. A.,Philp, Douglas,Harris, Kenneth D. M.
, p. 2338 - 2349 (2007/10/03)
A homologous series of bis-diphenylphosphine oxides (C6H5)2PO-(CH2)nPO(C 6H5)2 (with n = 2-8; denoted 2-8] have been investigated to explore the effects of a range of competing and cooperative intermolecular and intramolecular interactions on the structural properties in the solid state. The important factors influencing the structural properties include intramolecular aspects such as the conformation of the aliphatic chain and the intramolecular interaction between the two P=O dipoles in the molecule, and intermolecular aspects such as long-range electrostatic interactions (dominated by the arrangement of the P=O dipoles), C-H ... O interactions, C-H ... π interactions and π ... π interactions. Compounds 3 and 5 could be crystallized only as solvate co-crystals (3 · water and 5 · (toluene)2], whereas the crystal structures of all the other compounds contain only the bis-diphenylphosphine oxide molecule. The crystal structures have been determined from single-crystal X-ray diffraction data, with the exception of 7 (which has been determined here from powder X-ray diffraction data) and 4 (which was known previously). The compounds with even n represent a systematic structural series, exhibiting characteristic, essentially linear P=O ... P=O ... P=O dipolar arrays, together with C-H ... O and C-H ... π interactions. For the compounds with odd n, on the other hand, uniform structural behaviour is not observed across the series, although certain aspects of these crystal structures contribute in a general sense to our understanding of the structural properties of bis-diphenylphosphine oxides. Importantly, for the compounds with odd n, there is "frustration" with regard to the molecular conformation, as the preferred all-anti conformation of the aliphatic chain gives rise to an unfavourable parallel alignment of the two P=O dipoles within the molecule. Clearly the importance of avoiding a parallel alignment of the P=O dipoles becomes greater as n decreases. Local structural aspects (investigated by high-resolution solid-state 31P NMR spectroscopy) and thermal properties of the bis-diphenylphosphine oxide materials are also reported.
