Arsonium Research Articles

Phosphonium and arsonium salts based on alantolactone

The reaction of alantolactone, a sesquiterpene α,β-unsaturated lactone, with H-phosphonium or H-arsonium triflates proceeds as P–H or As–H addition at the terminal =CH2 moiety to afford novel triphenyl(sesquiterpenyl)phosponium or -arsonium triflates. Their diastereoisomerism at the formed C11 chiral center has been simulated by quantum chemical calculations.

Synthesis of arsonium salts and betaines based on triphenylarsine and ω-bromoalkanoic acids

The reactions between Ph3As and ω-bromoalkanoic acids with the length of polymethylene fragment n = 5, 7, 9 afford quaternary arsonium salts. Their treatment with alkali gives biologically active arsenobetaines. Solvent-free reactions of Ph3P or Ph3As with 2,3-dibromopropionic acid lead to the corresponding arsonium and phosphonium salts bearing (CH2)2COOH substituent.

Selective delivery of remarkably high levels of gadolinium to tumour cells using an arsonium salt.

The use of a triphenylarsonium vector for tumour cell-targeting leads to a dramatic increase in Gd3+ uptake in human glioblastoma multiforme cells by up to an order of magnitude over the isosteric triarylphosphonium analogue, with significant implications for 'theranostic' applications involving delivery of this important lanthanoid metal ion to tumour cells.

Keto‐stabilized Arsenic Ylides and their Coordination to Gold(I)

Three different arsonium salts were prepared by a solvent‐free method from Ph3As and the respective 2‐bromoacetophenones. These salts were deprotonated by NaOH to form keto‐stabilized arsenic ylides. The ylids react with [AuCl(tht)] affording gold(I) complexes containing the C‐bound ylide. The compounds were characterized by NMR spectroscopy, IR spectroscopy, and X‐ray diffraction.

A reaction of stabilized arsonium ylide of dicarboxylate ester with tropylium fluoroborate: An efficient strategy for ring contraction of cycloheptatriene

The coupling of vinylic ylide (3) synthesized from AsPh3 (2) and dimethyl acetylenedicarboxylate (DMAD) (1) with tropylium fluoroborate (4) in CH2Cl2 was found to give 3-phenyl-1,2-dicarbomethoxyprop-2-enylidentriphenyl arsonium salt (5) via ring contraction of cycloheptatriene. Treatment of the latter (5) with aqueous sodium hydroxide gives 3-phenyl-1,2-dicarbomethoxyprop-2-enylidentriphenylarsorane (6, Z-isomer), and this efficiently isomerized to E-isomer (7) under sunlight irradiation.

Bis(tetraphenylarsonium) hexafluoridotechnetate(IV) dihydrate: preparation, structure and spectroscopic analysis.

Reports of quadrivalent transition-metal fluoride salts containing bulky organic cations are limited. In this context, we prepared the bis(tetraphenylarsonium) hexafluoridotechnetate(IV) dihydrate salt, (C24H20As)2[TcF6]·2H2O, by a cation metathesis reaction of (NH4)2[TcF6] in water. This is the first report of an arsonium salt of the hexafluoridotechnetate(IV) dianion. (AsPh4)2[TcF6]·2H2O crystallizes in the triclinic space group P-1. The [TcF6]2- anion adopts a slightly distorted octahedral geometry with an average Tc-F bond length of 1.933 Å. The cyclic voltammogram of (AsPh4)2[TcF6]·2H2O in CH3CN shows a one-electron reversible oxidation wave at 1.496 V.

Synthesis of olefins via a Wittig reaction mediated by triphenylarsine

An arsine-mediated Wittig reaction for the synthesis of olefins is described. After heating triphenylarsine in the presence of an activated alkyl bromide for 30min, the resulting arsonium salt condensed with aldehydes in as little as 5min at room temperature, yielding the olefins in high yields. Aromatic, heteroaromatic, and alkyl aldehydes were all suitable substrates for this process.

Synthesis of carboxylate arsenobetaines based on (carboxyalkyl)triphenylarsonium halides

It has been found that the reaction of triphenylarsine with unsaturated carboxylic acids (acrylic, maleic, and itaconic ones) supposed to yield the arsenobetaines does not occur, in contrast to similar reactions of carboxylic acids with tertiary phosphines. However, the interaction of tertiary arsines with the halogenated carboxylic acids has resulted in the corresponding tertiary arsonium salts, dehydrohalogenation of the latter affording the target carboxylate betaines in the quantitative yield; the products structure has been elucidated using a set of chemical, physical, and physico-chemical methods. Antibacterial activity of the prepared compounds has been studied.

Oxidation of tris(2,4,6-triisopropylphenyl)phosphine and arsine

A reaction of the radical cation of tris(2,4,6-triisopropylphenyl)phosphine with oxygen gave a phosphonium salt resulting from the introduction of the oxygen atom to the phosphorus and the formation of a five membered ring by participation of the ortho isopropyl group. On the other hand, oxidation of the phosphine with mCPBA afforded the corresponding phosphine oxide. X-ray crystallography showed that the CPC bond angles and the PC bond lengths of the phosphine oxide are similar to those of the corresponding phosphine. The corresponding arsine underwent analogous reactions to afford the arsonium salt and the arsine oxide.

ChemInform Abstract: A Convenient Synthesis of Fluorine‐Containing trans‐1,2‐Cyclopropane Derivatives from Semistabilized Arsonium Ylides.

The fluorine-containing trans-1,2-cyclopropane derivatives 4ba–4dd were synthesized from the fluorine-containing electron-deficient alkenes 3a–3d with semistabilized arsonium ylides 2b–2d, in biphasic system of dichloromethane-50% aqueous sodium hydroxide, generated in situ from the corresponding arsonium salts 1b–1d at room temperature in good yields with high stereoselectivity. The structure of fluorine-containing trans-1,2-cyclopropane derivatives were also studied.

A Convenient Synthesis of Fluorine‐Containing trans‐1,2‐Cyclopropane Derivatives from Semistabilized Arsonium Ylides

AbstractThe fluorine‐containing trans‐1,2‐cyclopropane derivatives 4ba–4dd were synthesized from the fluorine‐containing electron‐deficient alkenes 3a–3d with semistabilized arsonium ylides 2b–2d, in biphasic system of dichloromethane‐50% aqueous sodium hydroxide, generated in situ from the corresponding arsonium salts 1b–1d at room temperature in good yields with high stereoselectivity. The structure of fluorine‐containing trans‐1,2‐cyclopropane derivatives were also studied.

Non-cross-linked polystyrene-supported triphenylarsonium halides and their use in the arsa-Wittig reaction

Non-cross-linked polystyrene-supported (carbomethoxymethyl)triphenylarsonium bromide ( 1) and benzyltriphenylarsonium iodide ( 2) were synthesized. They showed similar reactivities compared with the free arsonium salts in the arsa-Wittig reaction. The use of the polymer-supported reagents facilitated product purification and rendered the organoarsenic reagents easily separable and recyclable.

ChemInform Abstract: A Novel Double Elimination of Arsonium Salts. One-Pot Synthesis of 4- Trifluoromethyl-2,4-dienyl Carboxylates.

ChemInform Abstract: A Novel Double Elimination of Arsonium Salts. One-Pot Synthesis of 4- Trifluoromethyl-2,4-dienyl Carboxylates.

ChemInform Abstract: A Novel One-Pot Synthesis of 2,4-Enynyl Amides.

Abstract Silylated 2,4-enynyl amides can be synthesized by the reaction of 3-(trimethylsilyl)-2-propynylidenetriphenylarsorane, generated in situ from the corresponding arsonium salt and n-butyllithium, with α-bromoacetamides in 40–59% yields (two steps) and with high stereoselectivity.

ChemInform Abstract: Facile Syntheses of Unsaturated Aldehydes, Ketones, Amides, and Related Natural Products via Arsonium Salts

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: One‐Pot Approach for the Stereoselective Synthesis of Spirocyclopropyl Oxindoles from Isatins and Arsonium Salts.

AbstractThe trans‐products are obtained in high yields under mild conditions.

One-pot approach for the stereoselective synthesis of spirocyclopropyl oxindoles from isatins and arsonium salts

A one-pot approach for highly stereoselective synthesis of spirocyclopropyl oxindoles 3 with good to excellent yields from the reaction of isatins 1 and arsonium salts 2 in the presence of K 2CO 3 is described. The structure of product 3 was confirmed by 1H NMR, 13C NMR, IR, MS, EA, and X-ray diffraction as well.

ChemInform Abstract: Highly Stereoselective Synthesis of Cyclopropyl Heterocycles via Cyclopropanation of Olefin with Arsonium Salt.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Highly stereoselective synthesis of cyclopropyl heterocycles via cyclopropanation of olefin with arsonium salt

Abstractmagnified imageAn efficient and highly stereoselective approach for the preparation of highly functionalized cyclopropyl heterocycles via the cyclopropanation of olefines with arsonium salts in the presence of KF2H2O has been developed.

Comparative Study of the Phospha‐ and Arsa‐Wittig Reaction Using 1H, 75As and 17O NMR Spectroscopy

AbstractThe existence of oxaarsetanes during an arsa‐Wittig reaction has been proved by 1H and 17O NMR spectroscopy. 75As NMR spectra were obtained from the corresponding arsonium salts and arsane oxides. The dynamic 1H NMR spectra of phospha‐ and arsaylides were compared. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)