Hyperconjugation cyclic

Because the fluorine substituents both inductively and hyperconjugatively withdraw electron density from the C(2)-C(3) tt bond, the LUMO is located there, and Diels-Alder reactions take place exclusively with this bond [25] 1,1 -Difluoro allene and fluoroallene reaet readily with a large selection of cyclic and acyclic dienes, and acyclic dienes, [2+2] cycloadditions compete with the Diels-Alder processes As shown in the example in equation 79, a significantly different regiochemistry is observed for the [2+4] cycloaddition compared with the [2+2]... 

K Relaxation mechanism was also proposed [130-133], The % relaxation originates from cyclic delocalization of % electrons in the double bond through the hyperconjugation with a bonds on the saturated ring atoms under control of the orbital phase property [134, 135],... 

Intensities of Electronic Transitions in Molecular Spectra. IV. Cyclic Dienes and Hyperconjugation. J. chem. Physics 7, 339 (1939). 

Carbon and nitrogen are the most common elements from the first row of the periodic table to form aromatic compounds, characterized by cyclic electron delocalization. The bonding of these elements in the conjugated systems shows a large variety. Carbon can be a divalent (carbene), sp carbon with one jT-electron, but also sp carbon can be part of hyperconjugate aromatic systems, provided that it is properly substituted. The pyrrole- and pyridine-type nitrogens also allow the formation of cyclic electron delocalization in a large variety of aromatic systems. 

The UV photoelectron spectra of several chromans have been compared with other cyclic and acyclic ethers. The chroman spectra are clearly distinguishable from those of the other ethers and the differences have been interpreted in terms of the decreased conjugative effects of oxygen and increased hyperconjugative effects of the 4-methylene group (76T167). 

The cyclic form 7 had a stabilization of 74.4 kcalmol 1 relative to CH3+, the parallel form 8, 72.0 kcalmol-1, and the orthogonal form 9, 42.4 kcalmol-1. The lesser stability of the orthogonal form is attributable to the lack of hyperconjugation in this geometry. 

As with alkenes, in general, anti-addition is often the course of reaction, especially when halonium ions are involved109-112. However, as mentioned earlier, syn addition can take place in the bromination of /Tsilylslyrenes. This stereochemistry is explained by stabilization of the open-chain carbocation by the aromatic group, compared to the cyclic bromonium ion. In this case the conformer 83 has the maximum hyperconjugative stabilization, and is formed by the least motion rotation about the carbon-carbon bond. 

Some 2-alkoxytetrahydropyrans show a reactivity toward oxidants which parallels the reactivity of polycyclic amines discussed above, and which is in line with the hypothesis that weakening of C-H bonds by hyperconjugation should also increase the rate of C-H bond cleavage. For instance, of the two epimeric pyrans sketched in Scheme 2.15 only that with an axial 2-H is oxidized by ozone [51]. The same selectivity has been observed in the oxidation of methyl a- and /3-glucopyranoside with ozone [52], and in homolytic C-H bond cleavage in cyclic ethers [53],... 

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