We apply an orbital phase theory to the torquoselectivity of the electrocyclic reactions of 3-substituted (X) cyclobutenes. The torquoselectivity is shown to be controlled by the orbital-phase relation of the reacting pi(CC) and sigma(CC) bonds with the sigma(CX) bond geminal to the sigma(CC) bond to be cleaved. The inward rotation of electron-donating sigma(CX) bonds and outward rotation of electron-withdrawing sigma(CX) bonds have been deduced from the orbital-phase theory. Enhancement of the inward rotation by the electron-donating capability of the sigma(CX) bonds is confirmed by the correlation between the torquoselectivity and sigma(CX) orbital energy. The orbital overlaps between the geminal sigma(CX) (sigma(CH)) and sigma(CC) bonds are found to be important as well. Unsaturated substituents with low-lying unoccupied pi orbitals also promote the inward rotation. 相似文献
The groups with local symmetries are employed to explore the intrinsic symmetries of various kinds of cycloadditions to become apparent ones. For the electrocyclic reactions, the concept of local symmetry can still be applied equivalently, but no new result can be achieved. Furthermore, the local symmetries are generalized to the systems as a many body treatment performed by Matsen. 相似文献
Torquoselectivity in the electrocyclic interconversions of 1-azapolyenes and their heterocyclic isomers was investigated theoretically. The ring openings of 1,2-dihydroazete, 1,2-dihydropyridine, and 1,2-dihydroazocine were examined using HF, MP2, and B3LYP calculations. A large preference for inward rotation of the nitrogen lone pair and outward rotation of the N-H group was found for the four- and six-electron systems. No strong preference was observed for the eight-electron system. 相似文献
An unusual reaction manifold for cyclopropylcarbinyl cations, uncovered using B3LYP and MP2 calculations, is described. This reaction is a hybrid of a [1,2] sigmatropic hydrogen shift and a two-electron electrocyclic ring opening. These two processes occur through a single transition structure (i.e., they are concerted), although they are not synchronous. We call these reactions "hiscotropic" rearrangements. The potential energy surfaces for these reactions are often complicated, in some cases involving flat plateaus and bifurcations. Torquoselectivity occurs in some cases as a result of favorable orbital interactions between the breaking C-C and C-H bonds. 相似文献
There are many reports1 of the pyrolysis of fluorinated organic compounds, including the defluorination of cyclic fluorocarbons over iron to give aromatic compounds. Extending this technique we have investigated the flow pyrolysis of some readily accessible unsaturated fluorocarbons, such as I, II, and III, and found these to be synthetically useful routes to fluorinated dienes, cyclobutenes, and furans. Pyrolyses were carried out using a nitrogen flow over platinum, iron or caesium fluoride heated at 430–700°. The various products can all be rationalized in terms of intermediate allylic radicals, and the solid substrate influences which allylic radicals are formed.We are also investigating the chemistry of those now accessible compounds, such as IV, V, and VI, and some of the preliminary results are described. For example the fluoride ion induced dimerisation of IV gave two major products VII and VIII via a particular interesting mechanism. 相似文献
Differences in the Mulliken electronic overlap populations (due to electronic excitation) for pairs of centres undergoing bonding changes are suggested as a measure of reactivity in electrocyclic reactions. Good correlation of these quantities with the experimentally determined reactivity patterns was obtained for photocyclization in stilbenes, benzostilbenes and azastilbenes. 相似文献
The review considers the known strategies for the synthesis of fragments of arabinogalactan and lipoarabinomannan, polysaccharides that are contained in the cell walls of causative agent of tuberculosis Mycobacterium tuberculosis, as well as other related oligosaccharides containing arabinofuranose residues, using silyl substituents both for the differentiation of hydroxy groups in monosaccharide blocks and as stereodirecting groups during formation of a β-arabinofuranoside bond. In particular, the use of silyl groups (in combination with orthogonal to them acyl groups) allows the stereoselective synthesis of arabinans without the involvement of benzyl groups removable under reducing conditions, which is unacceptable in the presence of fragments sensitive to hydrogenolysis. This significantly simplifies the synthesis of 1,2-cis-linked oligosaccharides containing multiple bonds or azide groups, in particular, in aglycone, which is extremely important for the preparation of neoglycoconjugates both by converting the azide to an amine, followed by covalent binding to a carrier, and by conducting click-chemistry reactions using the 1,3-dipolar cycloaddition of azides to alkynes.
A novel organic/inorganic hybrid material comprising carboncoated cobalt nanoparticles and a poly(benzylchloride)styrene shell is the first magnetic support that complies with important requirements for immobilized reagents and scavengers, that is, stability under harsh conditions (e.g., acids), sufficient loading (up to 2 mmol g(-1)), and satisfying magnetization. The durability of the scaffold was demonstrated by immobilization of a trialkylsilane reagent, which served as a "magnetic" protecting group for a number of primary and secondary alcohols. Importantly, the scaffold could be efficiently separated, recycled, and reused after alcohol cleavage (HF·pyridine) via regeneration of the silyl chloride moiety with BCl(3). 相似文献
Transmetalation of carborane-fused zirconacycles to Cu(Ⅱ) induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carborane-fused cyclobutenes and cyclobutanes. A reaction mechanism involving transmetalation to Cu(Ⅱ) and reductive elimination is proposed. 相似文献
Photochemical pericyclic reactions are believed to proceed via a so-called pericyclic minimum on the lowest excited potential surface (S(1)), which is common to both the forward and backward reactions. Such a common intermediate has never been directly detected. The photointerconversion of 1,3-butadiene and cyclobutene is the prevailing prototype for such reactions, yet only diene ring closure proceeds with the stereospecificity that the Woodward-Hoffmann rules predict. This contrast seems to exclude a common intermediate. Using ultrafast spectroscopy, we show that the excited states of two cyclobutene/diene isomeric pairs are linked by not one, but by two common minima, p* and ct*. Starting from the diene side (cyclohepta-1,3-diene and cycloocta-1,3-diene), electrocyclic ring closure passes via the pericyclic minimum p*, whereas ct* is mainly responsible for cis-trans isomerization. Starting from the corresponding cyclobutenes (bicyclo[3.2.0]heptene-6 and bicyclo[4.2.0]octene-7), the forbidden isomer is formed from ct*. The path branches at the first (S(2)/S(1)) conical intersection towards p* and ct*. The fact that the energetically unfavorable ct* path can compete is ascribed to a dynamic effect: the momentum in C=C twist direction, acquired--such as in other olefins--in the Franck-Condon region of the cyclobutenes. 相似文献