Diels–Alder Cycloaddition on Nonisolated-Pentagon-Rule C2v(19 138)–C76 and YNC@C2v(19 138)–C76: The Difference in Regioselectivity Caused by the Inner Metallic Cluster

2019 ◽  
Vol 84 (22) ◽  
pp. 14571-14578
Author(s):  
Pei Zhao ◽  
Shuaifeng Hu ◽  
Xing Lu ◽  
Xiang Zhao
2020 ◽  
Author(s):  
Veejendra Yadav

The <i>endo</i> and <i>exo</i> stereoselectivities of the Diels-Alder (DA) cycloaddition reactions of 3,3-disubstituted cyclopropenes with butadiene and cyclopentadiene, the latter for the first time, were investigated by means of density functional and quantum chemical calculations for a comparison. To establish distinction between the selectivites, activation free energies were systematically estimated in the gas phase and also in solvents. The differential activation free energies clearly predict exclusive <i>endo</i> configuration of the products formed from the reaction of the unsubstituted cyclopropene with butadiene and cyclopentadiene. However, the results were found to be markedly different for the substituted cyclopropenes from available experimental selectivities. It was also discovered that butadiene and cyclopentadiene are markedly different in their respective stereospecific product yields, nevertheless the difference between the two was only a methylene group. The failure of the differential activation free energy approach to predict the experimental stereoselectivities of the DA reactions of several perhalocyclopropenes with cyclopentadiene is probably due to yet insufficient development of the various theoretical models dealing with the <i>endo</i> and <i>exo</i> DA preferences.


2014 ◽  
Vol 13 (06) ◽  
pp. 1450048 ◽  
Author(s):  
Sophia S. Borisevich ◽  
Alena V. Kovalskaya ◽  
Inna P. Tsypysheva ◽  
Sergey L. Khursan

A DFT study was performed for the Diels–Alder traction of 12-N-methylcytisine with a number of dienophiles (in boiling toluene under atmospheric pressure), namely, N-phenylmaleimide, maleic anhydride, 2,4-benzoquinone, tetracyanoethylene and methyl methacrylate. It was shown that 12-N-methylcytisine selectively reacts with these dienophiles, only the reaction with N-phenylmaleimide (NPM) resulting in the formation of thermodynamically stable adducts, which is consistent with experimental data. This selectivity of 12-N-methylcytisine is attributable to the difference between the properties of the listed dienophiles, which is confirmed by the relative reactivity indices calculated within the framework of the frontier molecular orbital (FMO) and hard and soft (Lewis) acids and bases (HSAB) theories, the thermodynamic and activation parameters of the forward and retro-Diels–Alder reactions. According to analysis of the theoretical results, NPM is characterized by high chemical potential, hardness close to that of 12-N-methylcytisine, and commensurable heights of the activation barriers for the forward and reverse Diels–Alder reactions and also forms stable [4+2] adducts.


2020 ◽  
Author(s):  
Veejendra Yadav

The <i>endo</i> and <i>exo</i> stereoselectivities of the Diels-Alder (DA) cycloaddition reactions of 3,3-disubstituted cyclopropenes with butadiene and cyclopentadiene, the latter for the first time, were investigated by means of density functional and quantum chemical calculations for a comparison. To establish distinction between the selectivites, activation free energies were systematically estimated in the gas phase and also in solvents. The differential activation free energies clearly predict exclusive <i>endo</i> configuration of the products formed from the reaction of the unsubstituted cyclopropene with butadiene and cyclopentadiene. However, the results were found to be markedly different for the substituted cyclopropenes from available experimental selectivities. It was also discovered that butadiene and cyclopentadiene are markedly different in their respective stereospecific product yields, nevertheless the difference between the two was only a methylene group. The failure of the differential activation free energy approach to predict the experimental stereoselectivities of the DA reactions of several perhalocyclopropenes with cyclopentadiene is probably due to yet insufficient development of the various theoretical models dealing with the <i>endo</i> and <i>exo</i> DA preferences.


2020 ◽  
Author(s):  
Veejendra Yadav

The <i>endo</i> and <i>exo</i> stereoselectivities of the Diels-Alder (DA) cycloaddition reactions of 3,3-disubstituted cyclopropenes with butadiene and cyclopentadiene, the latter for the first time, were investigated by means of density functional and quantum chemical calculations for a comparison. To establish distinction between the selectivites, activation free energies were systematically estimated in the gas phase and also in solvents. The differential activation free energies clearly predict exclusive <i>endo</i> configuration of the products formed from the reaction of the unsubstituted cyclopropene with butadiene and cyclopentadiene. However, the results were found to be markedly different for the substituted cyclopropenes from available experimental selectivities. It was also discovered that butadiene and cyclopentadiene are markedly different in their respective stereospecific product yields, nevertheless the difference between the two was only a methylene group. The failure of the differential activation free energy approach to predict the experimental stereoselectivities of the DA reactions of several perhalocyclopropenes with cyclopentadiene is probably due to yet insufficient development of the various theoretical models dealing with the <i>endo</i> and <i>exo</i> DA preferences.


1962 ◽  
Vol 14 ◽  
pp. 149-155 ◽  
Author(s):  
E. L. Ruskol

The difference between average densities of the Moon and Earth was interpreted in the preceding report by Professor H. Urey as indicating a difference in their chemical composition. Therefore, Urey assumes the Moon's formation to have taken place far away from the Earth, under conditions differing substantially from the conditions of Earth's formation. In such a case, the Earth should have captured the Moon. As is admitted by Professor Urey himself, such a capture is a very improbable event. In addition, an assumption that the “lunar” dimensions were representative of protoplanetary bodies in the entire solar system encounters great difficulties.


1997 ◽  
Vol 161 ◽  
pp. 491-504 ◽  
Author(s):  
Frances Westall

AbstractThe oldest cell-like structures on Earth are preserved in silicified lagoonal, shallow sea or hydrothermal sediments, such as some Archean formations in Western Australia and South Africa. Previous studies concentrated on the search for organic fossils in Archean rocks. Observations of silicified bacteria (as silica minerals) are scarce for both the Precambrian and the Phanerozoic, but reports of mineral bacteria finds, in general, are increasing. The problems associated with the identification of authentic fossil bacteria and, if possible, closer identification of bacteria type can, in part, be overcome by experimental fossilisation studies. These have shown that not all bacteria fossilise in the same way and, indeed, some seem to be very resistent to fossilisation. This paper deals with a transmission electron microscope investigation of the silicification of four species of bacteria commonly found in the environment. The Gram positiveBacillus laterosporusand its spore produced a robust, durable crust upon silicification, whereas the Gram negativePseudomonas fluorescens, Ps. vesicularis, andPs. acidovoranspresented delicately preserved walls. The greater amount of peptidoglycan, containing abundant metal cation binding sites, in the cell wall of the Gram positive bacterium, probably accounts for the difference in the mode of fossilisation. The Gram positive bacteria are, therefore, probably most likely to be preserved in the terrestrial and extraterrestrial rock record.


1994 ◽  
Vol 144 ◽  
pp. 421-426
Author(s):  
N. F. Tyagun

AbstractThe interrelationship of half-widths and intensities for the red, green and yellow lines is considered. This is a direct relationship for the green and yellow line and an inverse one for the red line. The difference in the relationships of half-widths and intensities for different lines appears to be due to substantially dissimilar structuring and to a set of line-of-sight motions in ”hot“ and ”cold“ corona regions.When diagnosing the coronal plasma, one cannot neglect the filling factor - each line has such a factor of its own.


Author(s):  
Jules S. Jaffe ◽  
Robert M. Glaeser

Although difference Fourier techniques are standard in X-ray crystallography it has only been very recently that electron crystallographers have been able to take advantage of this method. We have combined a high resolution data set for frozen glucose embedded Purple Membrane (PM) with a data set collected from PM prepared in the frozen hydrated state in order to visualize any differences in structure due to the different methods of preparation. The increased contrast between protein-ice versus protein-glucose may prove to be an advantage of the frozen hydrated technique for visualizing those parts of bacteriorhodopsin that are embedded in glucose. In addition, surface groups of the protein may be disordered in glucose and ordered in the frozen state. The sensitivity of the difference Fourier technique to small changes in structure provides an ideal method for testing this hypothesis.


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