Search results for "cyclopentadiene"
showing 10 items of 49 documents
An AM1 theoretical study on the effect of Zn2+ Lewis acid catalysis on the mechanism of the cycloaddition between 3-phenyl-1-(2-pyridyl)-2-propen-1-o…
2002
Abstract The mechanism of the Diels–Alder reaction between 3-phenyl-1-(2-pyridyl)-2-propen-1-one and cyclopentadiene has been investigated with the AM1 semiempirical method. Stationary points for two reactive channels, endo - cis and exo - cis , have been characterized. The role of the Lewis acid catalyst has been modeled taking into account the formation of a complex between Zn 2+ and the carbonyl oxygen atom and the pyridyl nitrogen atom of the 3-phenyl-1-(2-pyridyl)-2-propen-1-one system with and without the presence of two molecules of water around the cation. The mechanism of the uncatalyzed reaction corresponds to a concerted process, but in the presence of Lewis acid catalyst the mec…
Theoretical studies on cycloaddition reactions
2014
Cycloaddition reactions represent one of the most powerful processes in organic chemistry. The most common types of cycloaddition reactions are the Diels-Alder (DA) and the 1,3-dipolar cycloaddition reactions (1,3-DCs) which lead to five and six membered rings, respectively. In our ongoing efforts to contribute to the understanding of DA and 1,3-DCs; we studied the following using the B3LYP/6-31G(d) level of theory: 1. The 1,3-DCs of the pyridinium-3-olates and pyrazinium-3-olates with methyl acrylate and methyl methacrylate [1,2]. 2. The competitive hetero-DA and 1,3-DCs of methyl glyoxylate oxime and its tautomeric nitrone with cyclopentadiene in the absence and in the presence of BF3 as …
Understanding the formation of [3+2] and [2+4] cycloadducts in the Lewis acid catalysed reaction between methyl glyoxylate oxime and cyclopentadiene:…
2013
The formation of the formal [3+2] and [2+4] cycloadducts in the Lewis acid (LA) catalysed reaction of cyclopentadiene (Cp, 1) with methyl glyoxylate oxime (MGO, 2a) has been theoretically studied using DFT methods. Coordination of BF3 LA to the oxygen atom of MGO 2a not only increases the electrophilicity of the oxime, but also makes the corresponding tautomeric BF3:nitrone complex 8b the reactive species. The reaction is characterised by the nucleophilic attack of Cp 1 on the carbon atom of the corresponding BF3:nitrone complex 8b. The subsequent ring closure at the end of the reaction allows the formation of the [3+2] or [2+4] cycloadducts. ELF bonding analysis of selected points on the i…
Asymmetrische Hetero-Diels-Alder-Reaktionen in wäßriger Lösung unter Verwendung von Aminosäureestern als chiralen Auxiliaren
1989
(R)- und (S)-Aminosaure-methylester-hydrochloride bilden mit Formaldehyd in THF/Wasser-Gemischen Iminium-Ionen, die als elektronenarme Dienophile mit Cyclopentadien, 1,3-Cyclohexadien und Alkyl-substituierten Butadienen bereits bei 0°C Hetero-Diels-Alder-Reaktionen eingehen. Die Cycloaddukte werden mit hohen Ausbeuten im Multigrammasstab und mit Diastereomerenverhaltnissen (bis zu 93:7) gebildet, die mit anderen chiralen Aminen bisher nicht erreicht werden konnten. Mit Hilfe von NOE-Experimenten werden die absoluten Konfigurationen der Hauptdiastereomeren zugeordnet. Aus den Phenylglycin- und den Serin-Derivaten konnen die chiralen Hilfsgruppen mittels hydrogenolytischer Methoden bzw. unter…
ChemInform Abstract: Asymmetric Synthesis of Bicyclic Amino Acid Derivatives by Aza-Diels- Alder Reactions in Aqueous Solution.
2010
Derivatives 7–10 and 13–16 of methyl and ethyl 2-azabicyclo[2.2.1]heptane-3-carboxylates are synthesized by Aza-Diels-Alder reactions of chiral iminium ions, formed in situ from glyoxylic acid and chiral amines, with cyclopentadiene. Whereas the heterodienophiles derived from phenylglycinol and esters of sterically more demanding amino acids fail to undergo asymmetric cycloadditions, with alanine methyl ester and (R)-1-phenylethylamine hydrochoride the cycloadducts are formed in yields of 15 and 52%, respectively, reaching de values of up to 90:10 for the exo isomers.
ChemInform Abstract: (S)-Proline Benzyl Ester as Chiral Auxiliary in Lewis Acid-Catalyzed Asymmetric Diels-Alder Reactions.
1989
Asymmetric Diels-Alder reaction of cyclopentadiene (I) with (S)-proline benzyl ester (II) yields a mixture of the diastereomeric cycloadducts (R)-(III) and (S)-(IV).
Synthesis and characterization of the [Ru(η5-C5Me4CF3)(CO)2]2 and Ru6(μ3-H)(η2-μ4-CO)2(μ-CO)(CO)12(η5-C5Me4CF3) complexes
1998
The reaction of Ru3(CO)12 with tetramethyltrifluoromethylcyclopentadiene at various ratios of the reagents was studied. Refluxing of Ru3(CO)12 with a sixfold excess of tetramethyltrifluoromethylcyclopentadiene in octane in an inert atmosphere gave a complex, which is, according to X-ray diffraction data, a dimer,trans-[Ru(η5-C5Me4CF3)(CO)2]2. The reaction under the same conditions but starting from Ru3(CO)12 and C5Me4CF3H in 2∶1 molar ratio gave a hexaruthenium cluster [Ru6(μ3-H)(η2-μ4-CO)2(μ-CO)(Co)12(η5-C5Me4CF2)], which was characterized by IR as well as1H,13C, and19F NMR spectroscopy. According to X-ray diffraction data, an Ru4 tetrahedron, in which two edges are bound by additional “br…
Cycloaddition reactions of 2H-benzo[b]thiete and conjugated cyclic dienes
1996
2H-Benzo[b]thiete 1 reacts with cyclopentadiene 3 in consecutive [8π + 2π]cycloadditions yielding the condensed heterocycles 6–8. Tetracyclone 9 on the other hand gives only the monoadduct 10. An [8π + 8π]cycloaddition can be observed for 1 and diphenylisobenzofuran 11. The related π system 13 shows again consecutive [477π + 27π]processes (1 + 13 ← 14, 15).
A quantum chemical topological analysis of the c-c bond formation in organic reactions involving cationic species
2014
ELF topological analysis of the ionic Diels-Alder (I-DA) reaction between the N,N-dimethyliminium cation and cyclopentadiene (Cp) has been performed in order to characterise the C-C single bond formation. The C-C bond formation begins in the short range of 2.00-1.96 Åvia a C-to-C pseudoradical coupling between the most electrophilic center of the iminium cation and one of the two most nucleophilic centers of Cp. The electron density of the pseudoradical center generated at the most electrophilic carbon of the iminium cation comes mainly from the global charge transfer which takes place along the reaction. Analysis of the global reactivity indices indicates that the very high electrophilic c…
A Theoretical Study of the Reaction between Cyclopentadiene and Protonated Imine Derivatives: A Shift from a Concerted to a Stepwise Molecular Mecha…
2001
The reaction between cyclopentadiene and protonated pyridine-2-carboxaldehyde imine derivatives has been studied by using Hartree-Fock (HF) and B3LYP methods together with the 6-31G basis set. The molecular mechanism is stepwise along an inverted energy profile. This results from the protonation on both nitrogen atoms of the imine group and the pyridine framework. The first step corresponds to the nucleophilic attack of cyclopentadiene on the electron-poor carbon atom of the iminium cation group to give an acyclic cation intermediate, and the second step is associated with the ring closure of this intermediate via the formation of a C-N single bond yielding the final cycloadduct. Two reacti…