Search results for "Nucleophile"
showing 10 items of 385 documents
Quantitative ring contraction of 5-hydroxy-1,3-oxazin-2-ones into 5-hydroxymethyl-1,3-oxazolidin-2-ones: A DFT study
2007
Abstract The ring contraction of trans -5-hydroxy-1,3-oxazin-2-ones 1 into cis -5-hydroxymethyl-oxazolidinones 3 was studied with different bases and nucleophiles and it was found that it is the basicity and not the nucleophilicity the factor responsible for the ring contractions. A DFT study was made for the proposed mechanism.
ChemInform Abstract: Gold-Catalyzed Intramolecular Hydroamination of o-Alkynylbenzyl Carbamates: A Route to Chiral Fluorinated Isoindoline and Isoqui…
2013
Title compounds are prepared in enantiomerically pure form by the diastereoselective addition of fluorinated nucleophiles to N-(tert-butanesulfinyl)imines (I) followed by a sequence of Sonogashira cross-coupling/gold(I)-catalyzed cycloisomerization of the corresponding carbamate.
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…
An Understanding of the Electrophilic/Nucleophilic Behavior of Electro-Deficient 2,3-Disubstituted 1,3-Butadienes in Polar Diels−Alder Reactions. A D…
2008
The electrophilic/nucleophilic behavior of dimethyl 2,3-dimethylenesuccinate 1, an electron-deficient 2,3-disubstituted 1,3-butadiene, in polar Diels-Alder reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. The electronic nature of bonding of the transition structures involved in the cycloaddition reactions of the diene 1 toward the nucleophilically activated dienophile 6 and the strong electrophilically activated dienophile 7 has been carefully examined within the natural bond orbital (NBO) and the topological analysis of the electron localization function (ELF) frameworks. Additionally, a study of the global electrophilicity pattern of the reagents at the …
4-Chloro-1,1-diphenyl-3-(1-pyrrolyl)-2-azabuta-1,3-diene
2002
The title compound, C19H15ClN2, is the sole stable product resulting from nucleophilic attack of the sodium salt of pyrrole on 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene. The mechanism of its formation is briefly discussed.
Understanding the reactivity of captodative ethylenes in polar cycloaddition reactions. A theoretical study
2008
The electrophilic/nucleophilic character of a series of captodative (CD) ethylenes involved in polar cycloaddition reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. The transition state structures for the electrophilic/nucleophilic interactions of two CD ethylenes toward a nucleophilically activated ethylene, 2-methylene-1,3-dioxolane, and an electrophilically activated ethylene, 1,1-dicyanoethyelene, have been studied, and their electronic structures have been characterized using both NBO and ELF methods. Analysis of the reactivity indexes of the CD ethylenes explains the reactivity of these species. While the electrophilicity of the molecules accounts for…
Polycondensed nitrogen heterocycles. Part25. Aminopyrrolo[1,2-f]-phenanthridines by decomposition of 2-(3-azidophenyl)-1-arylpyrroles
1994
Acid catalyzed decomposition of the azido derivatives 4a-c gave rise to amino-hydroxy-phenylpyrroles of type 7 and 8 upon hydrolysis of the intermediate aryl nitrenium ions, together with the hydrogen abstraction compounds of type 3. The aminopyrrolo[1,2-f]phenanthridines 10, 11, and 12 were obtained by treatment with TFMSA of the azide 4d in which the ring being attacked was made more nucleophilic by the introduction of the methoxy group.
ChemInform Abstract: Polycondensed Nitrogen Heterocycles. Part 25. Aminopyrrolo(1,2-f) phenanthridines by Decomposition of 2-(3-Azidophenyl)-1-arylpy…
2010
Acid catalyzed decomposition of the azido derivatives 4a-c gave rise to amino-hydroxy-phenylpyrroles of type 7 and 8 upon hydrolysis of the intermediate aryl nitrenium ions, together with the hydrogen abstraction compounds of type 3. The aminopyrrolo[1,2-f]phenanthridines 10, 11, and 12 were obtained by treatment with TFMSA of the azide 4d in which the ring being attacked was made more nucleophilic by the introduction of the methoxy group.
1,5,7-Triazabicyclo[4.4.0]dec-1- ene (TBD), 7-Methyl-TBD (MTBD) and the polymer-supported TBD (P-TBD):Three efficient catalysts for the nitroaldol (H…
2000
Abstract The 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and its 7-methyl derivative (MTBD) have been proven to be of great synthetic utility as catalysts in the nitroaldol (Henry) reaction and for the addition of dialkyl phosphites to a variety of carbonyl compounds. The catalysts were in many cases superior to the parent tetramethylguanidine (TMG). In general the reaction proceeds in a few minutes at 0°C. The polymer-supported-TBD (P-TBD) was also proven to be an efficient promoter of the above cited nucleophilic additions.