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Dicationic Species (dicationic + species)

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Chemistry100%

Selected Abstracts

ChemInform Abstract: gem-Difluorination of Aminoalkynes via Highly Reactive Dicationic Species in Superacid HF,SbF5: Application to the Efficient Synthesis of Difluorinated Cinchona Alkaloid Derivatives.

CHEMINFORM, Issue 33 2008
Anne-Celine Cantet
Abstract ChemInform 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. [source]

Superacidic Activation of ,,,-Unsaturated Amides and Their Electrophilic Reactions

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2004
Konstantin Yu.
Abstract The electrophilic reactivity of ,,,-unsaturated amides towards weak nucleophiles such as arenes and cyclohexane, initiated either with triflic acid (CF3SO3H) or with excess AlCl3, has been studied. The amides generally condense readily with aromatics in the presence of AlCl3 to give 3-arylpropionamides and related compounds in excellent yields, while some amides also undergo selective ionic hydrogenation with cyclohexane to give saturated amides. The proposed mechanism of these reactions involves dicationic intermediates (superelectrophiles). The direct observation of a dicationic species (by low-temperature NMR) is reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Further Studies on the Synthesis of meso -Tetraarylazuliporphyrins under Lindsey,Rothemund Reaction Conditions and Their Conversion into Benzocarbaporphyrins

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2003
Timothy D. Lash
Abstract Azulene has been shown to react with pyrrole and a series of aromatic aldehydes in the presence of boron trifluoride etherate to give meso -tetraarylazuliporphyrins 6. Good yields of azuliporphyrins were obtained for benzaldehyde, 4-chlorobenzaldehyde, 4-bromobenzaldehyde, and 4-iodobenzaldehyde, and under dilute conditions p -tolualdehyde gave respectable yields. In each case, substantial amounts of meso -tetraarylporphyrins were also formed and a minor fraction of carbaporphyrin by-products could be detected, but otherwise no other macrocyclic products could be identified. 4-Nitrobenzaldehyde gave relatively poor yields of the corresponding azuliporphyrin, while p -anisaldehyde only gave trace amounts of product. Pentafluorobenzaldehyde gave variable results, although in this case a large number of additional by-products were identified including N -fused pentaphyrin, hexaphyrin, and higher order porphyrinoids, but no expanded azulene-containing macrocycles could be detected. Azuliporphyrins undergo reversible nucleophilic substitution on the seven-membered ring with pyrrolidine, benzenethiol, hydrazine, or benzylamine to give carbaporphyrin adducts. This property appears to facilitate an oxidative ring contraction of azuliporphyrins 6 with tert -butyl hydroperoxide in the presence of potassium hydroxide to produce mixtures of benzocarbaporphyrins 19 and 20. Tetraaryl-benzocarbaporphyrins exhibit slightly reduced diatropic ring currents compared to their meso -unsubstituted counterparts, although their UV/Vis spectra are very porphyrin-like and exhibit strong Soret bands near 450 nm. The benzocarbaporphyrins undergo reversible protonation to give monocationic and dicationic species. The latter involves C -protonation to generate an internal CH2 within the macrocyclic cavity. X-ray crystallography of tetraphenylbenzocarbaporphyrin 19a confirms that the preferred tautomer has the two NHs on either side of the indene subunit, in agreement with previous theoretical and spectroscopic studies. In addition, the presence of phenyl substituents at the 5,20-positions was found to tilt the indene moiety substantially by 27.4(1)° relative to the [18]annulene substructure. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Generation of Cationic [Zr-{tert -Butyl Enolate}] Reactive Species: Methyl Abstraction versus Hydride Abstraction

CHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2004
Bing Lian Dr.
Abstract Treatment of the neutral methyl,Zr,enolate [Cp2Zr(Me){O(tBuO)CCMe2}] (1) with one equivalent of B(C6F5)3 or [HNMe2Ph][B(C6F5)4] as a methyl abstractor in THF at 0,°C leads to the selective formation of the free ion pair complex [Cp2Zr(THF){O(tBuO)CCMe2}]+,[anion], (2) (anion=MeB(C6F5)3,, B(C6F5)4,), which is relevant to the controlled polymerization of methacrylates. Cation 2 rapidly decomposes at 20,°C in THF with release of one equivalent of isobutene to form the cationic Zr,carboxylate species [Cp2Zr(THF)(O2CiPr)]+ (3), through a proposed intramolecular proton transfer process from the tert -butoxy group to the enolate. The reaction of 1 with one equivalent of B(C6F5)3 or [HNMe2Ph][B(C6F5)4] in CH2Cl2 leads to the direct, rapid formation of the dimeric ,-isobutyrato,Zr dicationic species [{Cp2Zr[,-(O2CiPr)]}2]2+ (4), which gives 3 upon dissolution in THF. Contrastingly, when [Ph3C][B(C6F5)4] is used to generate the cationic Zr,enolate species from 1 in CD2Cl2, a 15:85 mixture of dicationic complexes 4 and [{Cp2Zr[, -(O2CC(Me)CH2)]}2]2+[B(C6F5)4] (5 -[B(C6F5)4]2) is obtained quantitatively. The formation of 5 is proposed to arise from initial hydride abstraction from a methyl enolate group by Ph3C+, as supported by the parallel production of Ph3CH, and subsequent elimination of methane and isobutene. In addition to standard spectroscopic and analytical characterizations for the isolated complexes 2,5, complexes 4 and 5 have also been structurally characterized by X-ray diffraction studies. [source]