Characterization of the switch in the mechanism of an intramolecular Diels-Alder reaction

Changing the dienophile moiety of an intramolecular Diels-Alder (IMDA) cycloaddition from an allyl ether to an allenyl ether can dramatically change the regioselectivity. We hereby show by density functional theory computations that such unprecedented divergence is produced by an underlying change in the mechanism of the reaction. The allyl ether yields a fused tetrahydrofuran through a classical Diels-Alder reaction, whereas the allenyl ether yields a (methylidene)tetrahydropyran through a stepwise process. The latter reaction involves an extreme asynchronism in the bond-forming events with a diradicaloid intermediate that is stabilized by conjugation and synergistic (captodative) effects. Comparison with intermolecular model D-A reactions, which are concerted processes with various degrees of asynchrony, helps explain the change in regioselectivity for the IMDA reaction of allyl systems and the shift in mechanism for the IMDA reaction of the allenyl derivatives studied.     

Pseudopericyclic design drives antara-antara [1,5] methylene sigmatropic shifts from a stepwise to a concerted mechanism

Antara-antara [1,5]-methylene sigmatropic shifts of propenylidene cyclopropane and its heteroanalogues are shown to proceed through concerted or stepwise mechanisms depending on a delicate balance that is directly related to the presence or absence of heteroatoms at the termini atoms of the rearrangement. Lowering of activation energies upon heteroatom replacement are more significant for the oxacyclopropane analogues 1D, 1E, and 1F but double heterosubstitution is still needed to achieve a pseudopericyclic reaction. In fact only after reaching a pseudopericyclic process the energy balance favors the concerted pathway. Negligible NICS values and a clear disconnection in the ACID plot as well as some structural and energetical parameters reveal the pseudopericyclic nature of this concerted antara-antara [1,5](CH(2) ) sigmatropic shift. Although the product of the pseudopericyclic process is unprecedented, similar cycloisomerizations after allene activation should be considered within this hitherto undescribed reactions.     

Cyclization cascade of allenyl azides: a dual mechanism

A density functional theory based computational approach to describing the mechanistic course of the allene azide cycloaddition cascade sequence has been developed. The results of these calculations permit characterization of key reactive intermediates (diradicals and/or indolidenes) and explain the different behaviors observed in the experimental studies between conjugated and nonconjugated species. Furthermore, computational analysis of certain intermediates offer insight into issues of regioselectivity and stereoselectivity in cases where different reaction channels are in competition, suggesting suitable substitutions to achieve a single regioisomer in the indole synthesis via azide-allene cyclization.     

Normal‐to‐Abnormal NHC Rearrangement of AlIII,GaIII, and InIII Trialkyl Complexes: Scope,Mechanism, Reactivity Studies,and H2 Activation

The present contribution reports experimental and theoretical mechanistic investigations on a normal‐to‐abnormal (C2‐to‐C4‐bonded) NHC rearrangement processes occurring with bulky group 13 metal NHC adducts, including the scope of such a reactivity for Al compounds. The sterically congested adducts (nItBu)MMe₃ (nItBu=1,3‐di‐tert‐butylimidazol‐2‐ylidene; M=Al, Ga, In; 1 a – c ) readily rearrange to quantitatively afford the corresponding C4‐bonded complexes (aItBu)MMe₃ ( 4 a – c ), a reaction that may be promoted by THF. Thorough experimental data and DFT calculations were performed on the nNHC‐to‐aNHC process converting the Al‐nNHC ( 1 a ) to its aNHC analogue 4 a . A nItBu/aItBu isomerization is proposed to account for the formation of the thermodynamic product 4 a through reaction of transient aItBu with THF–AlMe₃. The reaction of benzophenone with (nItBu)AlMe₃ afforded the zwitterionic species (aItBu)(CPh₂‐O‐AlMe₃) ( 6 ), reflecting the unusual reactivity that such bulky adducts may display. Interestingly, the nItBu/Al(iBu)₃ Lewis pair behaves like a frustrated Lewis pair (FLP) since it readily reacts with H₂ under mild conditions. This may open the way to future reactivity developments involving commonly used trialkylaluminum precursors.     

On the memory of chirality in gold(I)-catalyzed intramolecular carboalkoxylation of alkynes

A computational study of the mechanism of the intramolecular carboalkoxylation of alkynes reported by Toste et al. allows the characterization of the chirality transfer process that makes this reaction enantioselective. Memory of chirality is preserved up until the stereocenter-generating iso-Nazarov cyclization through the synergy between the helicity of a pentadienyl cation intermediate and the control in the conformation of the allyl group, both elements defined upon alkoxy migration. The high barriers to conformational scrambling relative to those corresponding to chemical steps ensure the robustness of the chirality transfer mechanism and result in an unusual importance of conformational changes in reactivity that seems to be common in gold-catalyzed transformations.     

Fuzzy control of original UPOs of unknown discrete chaotic systems

This paper presents a fuzzy algorithm for controlling original unstable periodic orbits of unknown discrete chaotic systems. In the modeling phase, only input–output data pairs provided from the true system are required. The fuzzy model is developed using Gaussian membership functions and consequent functions where the Levenberg–Marquardt computational algorithm is employed for the model parameters calculation. In the controller design phase, the L₂-stability criterion is used, which forms the basis of the main design principle. Simulation results are given to illustrate the effectiveness and control performance of the proposed method.     

Kinetic Instability of Anisotropic Drift Wave Accompanied by Field Aligned Currents in Solar Coronal Loop

Solar coronal loops are frequently accompanied by the field-aligned currents, which drive instabilities if the drift velocity u₀> v_A the Alfvén velocity. For our choice of parameters, the critical threshold value of u₀/v_A is~3.0 for growth and the corresponding current filling factor~10^-3-10^-4. Below this value we are no longer in the kinetic regime. The coronal loops also have short-scale density gradients within each loop. The electron resonance in the presence of density gradient causes the drift mode to grow. We study the effect of these two free energy sources, the electron drift and the density gradient, in the presence of temperature anisotropy T_⊥α > T_||α. These effects simultaneously exist in the coronae. Using gyrokinetic theory, we investigate the influence of these effects, examine how they interplay with each other and study the consequent growth of the magnetosonic wave. We observe that kinetic instability driven by density gradient can be suppressed by field-aligned currents. The temperature anisotropy with chosen signatures causes further stabilizing effect. The results may prove useful to study the heating mechanism of solar coronal loops, acceleration of particles and confinement of particles in the thermonuclear reactors.     

Growth-controlled synthesis of polymer-coated colloidal-gold nanoparticles using electrospray-based chemical reduction

In this study,the controlled nucleation and growth of gold nanoparticles(GNPs)were investigated using a self-repelled mist in a liquid chemical reaction environ...     

Biocompatibility of some materials used in dental implantology: histological study

This study deals with bioreactive materials for potential applications as endosseus dental implants. Currently used dental implants are made of dental alloys but due to cytotoxic problems, high strength ceramic materials appear as an interesting alternative to these alloys. In order to combine good mechanical properties and promotion of the osteointegration process, a ceramic composite material composed of 10 wt.% tricalcium phosphate (TCP) mixed with partially stabilized zirconia has been elaborated. Such a ceramic has been implanted into albino rats, the sites of implantation being the adrenal gland for the toxicity evaluation and the sphenoid bone to estimate the osteogenesis potential. These results have been compared to those obtained with implants made of alumina (Al₂O₃), zirconia (ZrO₂) or poly(ethylene terephthalate) (Dacron®). In all cases no rejection effect was observed. The histological study indicated that ZrO₂-TCP ceramics induced a marginal and subjacent cell disorganization. However, the existence of an irregular cellular band indicated a cellular colonization process on the TCP particles. The microscopy study of the implants after removal confirmed the bioresorption of TCP.