Search results for "Alder"
showing 10 items of 273 documents
ChemInform Abstract: Gold Catalyzed Stereoselective Tandem Hydroamination-Formal Aza-Diels-Alder Reaction of Propargylic Amino Esters.
2013
The overall sequence of the tandem reaction presented here leads to nitrogen-containing tetracycles under formation of 4 bonds and five stereocenters, in most cases as single diastereoisomers.
Gold-Catalyzed Tandem Hydroamination/Formal Aza-Diels-Alder Reaction of Homopropargyl Amino Esters: A Combined Computational and Experimental Mechani…
2015
A tandem gold-catalyzed hydroamination/formal aza-Diels-Alder reaction is described. This process, which employs quaternary homopropargyl amino ester substrates, leads to the formation of an intrincate tetracyclic framework and involves the generation of four bonds and five stereocenters in a highly diastereoselective manner. Theoretical calculations have allowed us to propose a suitable mechanistic rationalization for the tandem protocol. Additionally, by studying the influence of the ligands on the rate of the gold-catalyzed reactions, it was possible to establish optimum conditions in which to perform the process with a variety of substituents on the amino ester substrates. Notably, the …
A joint action of deep eutectic solvents and ultrasound to promote Diels−Alder reaction in a sustainable way
2020
The need to reduce environmental impact of chemical processes has induced a surge of attention in the choice of solvent and methodologies to carry them out. In this context, we studied the Diels−Alder reaction using N-ethylmaleimide as dienophile and changing the nature of the diene in deep eutectic solvents (DES) under both conventional heating and ultrasonic activation. DES obtained by the combination of different hydrogen bond acceptors and donors allowed assessing the role played by solvent nature. DES proved suitable solvent media for the target reaction, allowing higher yields and faster reactions compared to conventional organic solvents. The trend of yields, both in silent and under…
Computational strategies for the design of new enzymatic functions
2015
In this contribution, recent developments in the design of biocatalysts are reviewed with particular emphasis in the de novo strategy. Studies based on three different reactions, Kemp elimination, Diels–Alder and Retro-Aldolase, are used to illustrate different success achieved during the last years. Finally, a section is devoted to the particular case of designed metalloenzymes. As a general conclusion, the interplay between new and more sophisticated engineering protocols and computational methods, based on molecular dynamics simulations with Quantum Mechanics/Molecular Mechanics potentials and fully flexible models, seems to constitute the bed rock for present and future successful desig…
New structural aspects of 3-vinyl-1H-indoles for predicting the outcome of Diels-Alder reactions
1989
Some selected 3-vinyl-1H-indoles have been synthesised and the first13C-NMR studies performed; in addition He(Iα) photoelectron spectra and the results of perturbation MO calculations of some examples of this class of compounds are presented. The molecular characteristics obtained thereby can be used to predict the results of [π4s+π2s]-cycloaddition reactions with 3-vinylindoles.
ChemInform Abstract: Diels-Alder Reactions of (1H-Indol-3-yl)-enacetamides and -endiacetamides: A Selective Access to Acetylamino-Functionalized (b)A…
2010
Understanding the local reactivity in polar organic reactions through electrophilic and nucleophilic Parr functions
2013
[EN] Building upon our recent studies devoted to the bonding changes in polar reactions [RSC Advances, 2012, 2, 1334 and Org. Biomol. Chem., 2012, 10, 3841], we propose herein two new electrophilic, P-k(+), and nucleophilic, P-k(-), Parr functions based on the spin density distribution at the radical anion and at the radical cation of a neutral molecule. These local functions allow for the characterisation of the most electrophilic and nucleophilic centres of molecules, and for the establishment of the regio- and chemoselectivity in polar reactions. The proposed Parr functions are compared with both, the Parr-Yang Fukui functions [J. Am. Chem. Soc. 1984, 106, 4049] based on frontier molecul…
N-benzoylindole-2,3-quinodimethane: Diels-Alder reactivity and synthetic applications for [b]annellated indoles
1991
Abstract The Diels-Alder reactivity of in situ generated N -benzoylindole-2,3-quinodimethane has been expanded considerably to include reactions with carbon- and hetero-dienophiles which furnish a variety of [ b ]annellated indoles as well as functionalized and annellated carbazoles. The frontier molecular orbital theory was found to be a useful model for the prediction of the experimental results under consideration of reactivity aspects.
A density functional theory study for the Diels–Alder reaction between N-acyl-1-aza-1,3-butadienes and vinylamines. Lewis acid catalyst and solvent e…
2002
Abstract The molecular mechanism for the Diels–Alder reaction of N-acyl-1-aza-1,3-butadiene with dimethylvinylamine has been studied using density functional theory methods. This cycloaddition is the nucleophilic attack of the vinylamine to the conjugate position of the unsaturated acyl imine with concomitant ring-closure. The presence of a Lewis acid catalyst coordinated to the acyl oxygen atom decreases markedly the activation energy associated to the nucleophilic attack. This results from an increasing of the electrophilicity of the 1-aza-1,3-butadiene that shift the mechanism from a highly asynchronous concerted process to a polar stepwise one.
Density functional theory study of the Lewis acid-catalyzed Diels-Alder reaction of nitroalkenes with vinyl ethers using aluminum derivatives
2002
The inverse electron demand Diels–Alder reaction of nitroalkenes with vinyl ethers catalyzed by Lewis acids based on aluminum metal, AlMe3, Al(OMe)3 and AlCl3 was studied using density functional theory methods. A continuum model was selected to represent the effects of dichloromethane used as solvent. For this cycloaddition reaction two reactive channels corresponding to the endo and exo approach modes of the vinyl ether to the Lewis acid-coordinated nitroalkene were studied. Coordination of the aluminum metal to an oxygen atom of the nitroalkene increases the electrophilicity of the heterodiene, decreasing the activation energy of the cycloaddition. The substitution effect on the aluminum…