Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity

Indexación: Web of ScienceTheoretical reactivity indices based on the conceptual Density Functional Theory (DFT) have become a powerful tool for the semiquantitative study of organic reactivity. A large number of reactivity indices have been proposed in the literature. Herein, global quantities like the electronic chemical potential μ, the electrophilicity ω and the nucleophilicity N indices, and local condensed indices like the electrophilic and nucleophilic Parr functions, as the most relevant indices for the study of organic reactivity, are discussed.http://www.mdpi.com/1420-3049/21/6/74

Describing the molecular mechanism of organic reactions by using topological analysis of electronic localization function

Here, we provide an essay on the analysis of the reaction mechanism at the molecular level; in particular, the evolution of the electron pair, as it is provided by the ELF, is used to decribe the reaction pathway. Then, the reaction mechanism is determined by the topological changes of the ELF gradient field along a series of structural stability domains. From this analysis, concepts such as bond breaking/forming processes, formation/annihilation of lone pairs and other electron pair rearrangements arise naturally along the reaction progress simply in terms of the different ways of pairing up the electrons. To visualize these results some organic reaction mechanisms (the thermal ring aperture of cyclobutene and cyclohexa-1,3-diene) have been selected, indicating both the generality and utility of this type of analysis

A Combined Experimental and Theoretical Study of the Ammonium Bifluoride Catalyzed Regioselective Synthesis of Quinoxalines and Pyrido[2,3-b]pyrazines

International audienceAmmonium bifluoride was efficiently used (at a 0.5 mol % loading) to catalyze the cyclocondensation between 1,2-arylenediamines and 1,2-dicarbonyl compounds at room temperature in methanol-water, affording quinoxalines and pyrido[2,3-b]pyrazines in excellent yields. Importantly, 2,8-disubstituted quinoxalines and 3-substituted pyrido[2,3-b]pyrazines were regioselectively formed by reacting aryl glyoxals with 3-methyl-1,2-phenylenediamine and 2,3-diaminopyridine, respectively. Analysis of the DFT reactivity indices allowed to explain the catalytic role of ammonium bifluoride

Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system

[EN] The thermal and Lewis acid (LA) catalyzed cyclizations of quinone 1 involved in the synthesis of Colombiasin A and Elipsaterosin B have been theoretically studied using DFT methods at the B3LYP/6-311G(d,p) computational level. B3LYP calculations suggest that the formal endo [4 + 2] cycloadduct allowing the synthesis of Colombiasin A is preferentially formed under thermal conditions, while in the presence of the BF3 LA catalyst the formal [5 + 2] cycloadduct is seen, allowing the synthesis of Elipsaterosin B. The BF3 LA catalyst not only accelerates the nucleophilic attack on the C2 carbon of the quinone framework through a more polar C-C bond formation, but also provokes a different electron density rearrangement along the nucleophilic attack favoring the subsequent C-C bond formation at the C4 carbon with the formation of the formal [5 + 2] cycloadduct. ELF bonding analysis along these cyclizations indicates that the C-C single bond formation takes place in the range of 1.91-2.1 angstrom by C-to-C coupling of two pseudoradical centers. Along the formation of the first C2-C9 single bond, these pseudoradical centers appear at one of the most electrophilic and at one of the most nucleophilic centers of quinone 1, C2 and C9 carbons, respectively. Analysis of the Parr functions suggests that although the most favorable electrophilic/nucleophilic interaction is that involving the C2 carbon of quinone and the C12 carbon of the butadiene framework, the intramolecular nature of the cyclization prevents the corresponding reactive channel.This work was supported by the Post-Doctoral fellow FONDECYT Grant 3130359 and Project ICM-P10-003-F CILIS granted by Fondo de Innovacion para la Competitividad del Ministerio de Economia, Fomento y Turismo, Chile.Soto-Delgado, J.; Sáez-Cases, JA.; Tapia, RA.; Domingo, LR. (2013). Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system. Organic and Biomolecular Chemistry. 11(48):8357-8365. https://doi.org/10.1039/c3ob41860jS83578365114

Polar [3 + 2] cycloaddition of ketones with electrophilically activated carbonyl ylides. Synthesis of spirocyclic dioxolane indolinones.

International audienceThe [3 + 2] cycloaddition reaction between carbonyl ylides generated from epoxides and ketones (ethyl pyruvate, ethyl phenylglyoxylate, isatin, N-methylisatin and 5-chloroisatin) to give substituted dioxolanes and spirocyclic dioxolane indolinones was investigated. The effect of microwave irradiation on the outcome of the reaction was studied. The thermal reaction between 2,2-dicyano-3-phenyloxirane and N-methylisatin was theoretically studied using DFT methods. This reaction is a domino process that comprises two steps. The first is the thermal ring opening of the epoxide to yield a carbonyl ylide intermediate, whereas the second step is a polar [3 + 2] cycloaddition to yield the final spiro cycloadducts. The cycloaddition presents a low stereoselectivity and a large regio- and chemoselectivity. Analysis of the electrophilicity values and the Fukui functions of the reagents involved in the cycloaddition step allowed the chemical outcome to be explained

Formation of Pyrazol-1,3,4-Thiadiazoles through 1,3-Dipolar Cycloadditions of 3-Thioxo-[1,2,4]-Triazepin-5-one with Nitrilimines: An Experimental and Computational study

In this work the results of experimental and computational study of the title compounds and some ancillary compounds are reported. Two bicyclic pyrazol-1,3,4-thiadiazole derivatives were synthesized by reaction between 6-dimethylaminomethylene-3-thioxo-[1,2,4]- triazepin-5-one 1 and several nitrilimines 2a-f to give corresponding spirocycloadducts 3a-f, which undergo a rapid rearrangement leading to the new bicyclic compounds, 4a-f and 5a-f. These obtained bicyclic products were characterized by 1H and 13C NMR spectroscopy and finally by X-ray crystallography. Theoretical calculations have been carried out using DFT methods to rationalize the formation of the two new bicyclic compounds. Two reaction types are involved in the formation of the compounds 4a-f and 5a-f. The first one is a 1,3-dipolar cycloaddition reaction between 1 acting as dipolarophile and 2a-f as dipoles. The results indicate that the cycloaddition between 1 and 2g, as model of 2a-c, takes place via a high asynchronous bond-formation process. The regioselectivity obtained from the calculations is in complete agreement with the formation of the unique spirocycloadducts 3a-f. The second reaction leading to the formation of the final products is a domino process that is initiated by the quick and irreversible cleavage in a catalytic acid environment of triazepenic ring

Gravity modeling of the lithosphere in the Calatrava Volcanic Province (Spain): geodynamic implications

The origin of the intraplate volcanism in the Calatrava Volcanic Province (CVP) is controversial. On the basis of its geochemical signature it has been ascribed to an “aborted” rift, implying lithospheric thinning. However, the volcanism occurred during the generalized Cenozoic NW−SE-oriented compressive tectonic regime. On the other hand, on the basis of evidence for its deep-seated origin, it has been linked to the existence of a baby-plume detached from an active megaplume below the Canary-Azores Islands and the western Mediterranean. In order to understand better the aforementioned geodynamic scenarios for the origin of the CVP, we address here the study of the lithosphere in the CVP and its vicinity by means of gravity analysis and 2+1/2D modeling. Gravity modeling results do not support the rifting model adopted for the intraplate volcanism occurred in the CVP because the crust shows a constant thickness. Density models suggest the existence of a sub-crustal, anomalous low-density block that could be underplated magmatic material at the base of the crust, suggesting that only a minor part of it intruded up into the crust and erupted. The localized magmatism of the CVP can be related to the combination of two factors: one active, the gentle folding of the Iberian lithosphere and associated uplifting of the Variscan basement due to the NW-directed transmission of compressive stresses in the upper plate yielded by the subduction/collision in the south Iberian margin. The formation of the lithospheric folding in the Calatrava region results in a decrease of the pressure beneath the swell of the antiform that is likely to bring about basaltic magmatism below the swell; and one passive, the existence of a Variscan right-lateral shear band, which yields a weakened  crust that facilitates the ascent of the magmatic materials. The relatively small volume, but large extension, of the volcanic outcrops could be associated with the preferential ascent of the magmas along the weakened crust of this NW−SE-trending Variscan shear band.El origen del volcanismo intraplaca en la Provincia Volcánica de Calatrava (CVP) es controvertido. En base a su signatura geoquímica se ha atribuido a la formación de un rift “abortado”, implicando un adelgazamiento litosférico. Sin embargo, el volcanismo se desarrolló durante un régimen tectónico compresivo orientado NW-SE que fue generalizado en la región de Calatrava durante el Cenozoico. Por otro lado, en base a las evidencias de su origen profundo, se le ha relacionado con la existencia de una mini-pluma desconectada de una mega-pluma activa debajo de los archipiélagos de Canarias y Azores, y en el Mediterráneo occidental. Con el propósito de contribuir a la discriminación entre los escenarios geodinámicos mencionados para el origen del volcanismo se ha abordado aquí el estudio de la litosfera en la CVP y en las zonas próximas mediante el análisis gravimétrico y la modelación 2+1/2D. Los modelos gravimétricos no apoyan el modelo de rifting adoptado para el volcanismo intraplaca ocurrido en la CVP porque el espesor de la corteza es cuasi-constante. Los modelos siguieren la existencia de un cuerpo anómalo sub-cortical de baja densidad que podría ser material magmático acrecionado y almacenado en la base de la corteza indicando que sólo una parte menor habría intruido en la corteza y producido erupciones. El volcanismo localizado de la CVP se puede relacionar con la combinación de dos factores: a) Un factor activo correspondiente a un amplio plegamiento de la litosfera (corteza) Ibérica y el consiguiente levantamiento asociado del basamento varisco debido a la transmisión hacia el NW de los esfuerzos compresivos en la placa superior de la subducción/colisión miocena en el margen meridional Ibérico. La formación del anticlinal a escala cortical en la región de Calatrava ha producido la disminución de la presión en el intrados del anticlinal y ha originado probablemente el magmatismo basáltico; b) Un factor pasivo correspondiente a la existencia de una banda de cizalla con dirección próxima a NW-SE, heredada de la deformación varisca, que localiza una zona de debilidad cortical favorecedora del ascenso del magmatismo

A combined experimental and theoretical study of the polar [3+2] cycloaddition of electrophilically activated carbonyl ylides with aldehydes and imines

International audienceNumerous 2,5-diaryl-1,3-dioxolane-4,4-dicarbonitriles and 2,4-diphenyl-1,3-oxazolidine-5,5- dicarbonitriles have been synthesized by [3+2] cycloaddition reactions between carbonyl ylides generated from epoxides, and aldehydes or imines. In contrast to the use of aldehydes (3,4,5- trimethoxybenzaldehyde, piperonal, 1-naphthaldehyde, indole-3-carboxaldehyde, furan-2- carboxaldehyde and thiophene-2-carboxaldehyde), the reactions performed with imines (N- (phenylmethylene)methanamine, N-(1,3-benzodioxol-5-ylmethylene)propylamine, N-(1,3-benzodioxol- 5-ylmethylene)butylamine and N-(1,3-benzodioxol-5-ylmethylene)benzylamine) proceed diastereoselectively. The effect of microwave irradiation on the outcome of the reaction was studied. The mechanism of these [3+2] cycloaddition reactions has been theoretically investigated using DFT methods. These cycloadditions, which have one-step mechanisms, consist of the nucleophilic attack of the aldehyde oxygen or imine nitrogen on the carbonyl ylide. For the reaction with aldehydes, a back donation effect is responsible for the unexpected reverse charge transfer found at the transition structure. The analysis of the reactivity indices indicates that the large electrophilic character of the carbonyl ylides induces them to act as strong electrophiles in these polar [3+2] cycloaddition reactions