Hyperconjugation and

How do you interpret the values of p and r in these equations Which system is more sensitive to the aryl substituent How would you explain this difference in sensitivity Sketch the resonance, field and hyperconjugative interactions which you believe would contribute to these substituent effects. What, if any, geometric constraints would these interactions place on the ions ... 

The 1,3-dipolar cycloadditions offluonnatedallenes provide a rich and varied chemistry Allenes, such as 1,1-difluoroallene and fluoroallene, that have fluorine substitution on only one of their two cumulated double bonds are very reactive toward 1,3-dipoles Such activation derives from the electron attracting inductive and hyperconjugative effects of the allylic fluorine substituent(s) that give nse to a considerable lowering of the energy of the LUMO of the C(2)-C(3) n bond [27]... 

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]... 

The free t-butyl cation [7" ] in the gas phase is nothing more than a species detectable by the electron impact method (Yeo and Williams, 1970). However, it is not only an observable species by nmr studies in SbFs/FSOsH (Olah et al., 1964), but can be isolated from the solution in the form of its SbF or Sb2Ffi salt (Olah and Lukas, 1967a,b Olah et al., 1973 Yannoni et al., 1989). The crystal structure shows that this ion is planar and its carbon-carbon bonds are shortened to 144.2 pm (Hollenstein and Laube, 1993). Its particular electronic stabilization among aliphatic carbocations is attributed by physical organic chemists to the operation of both inductive and hyperconjugative effects in the cr bond system. 

This stereoelectronic effect also explains the contrasting regioselectivity of cis- and fra x-2-fluoro-4-f-butylcyclohexanone.235 As a result of a balance between its polar effect and hyperconjugation, the net effect of a fluoro substituent in acyclic systems is small. However, in 2-fluorocyclohexanones an unfavorable dipole-dipole interaction comes into play for the cis isomer and preferential migration of the fluoro-substituted carbon is observed. 

As a result of the inductive and hyperconjugative effects it is to be expected that tertiary carbonium ions will be more stable than secondary carbonium ions, which in turn will be more stable than primary ions. The stabilization of the corresponding transition states for ionization should be in the same order, since the transition state will somewhat resemble the ion. Thus the first order rate constant for the solvolysis of tert-buty bromide in alkaline 80% aqueous ethanol at 55° is about 4000 times that of isopropyl bromide, while for ethyl and methyl bromides the first order contribution to the hydrolysis rate is imperceptible against the contribution from the bimolecular hydrolysis.217 Formic acid is such a good ionizing solvent that even primary alkyl bromides hydrolyze at a rate nearly independent of water concentration. The relative rates at 100° are tertiary butyl, 108 isopropyl, 44.7 ethyl, 1.71 and methyl, 1.00.218>212 One a-phenyl substituent is about as effective in accelerating the ionization as two a-alkyl groups.212 Thus the reactions of benzyl compounds, like those of secondary alkyl compounds, are of borderline mechanism, while benzhydryl compounds react by the unimolecular ionization mechanism. 

FIGURE 10. Correlation diagram showing the influence of non-bonded through-space (n.bd.th.sp) interaction between the pseudo w-orbitals. t(( IU ) (circles) and the double-bond tr-orbitals tra and (ovals) on the 7r-orbital energies of the butadiene w-system. Aa is the basis energy of tra and 7Tb and SA the inductive and hyperconjugative destabilization (see equation 34)... 

TABLE 5. Inductive and hyperconjugative parameters for Me3M in Me3MCH2Ph and changes in C—M orbital energy due to hyperconjugative... 

Table 3.22. Some C=C bond orders, 7tcc polarization, ncc and 7tcc NLMOs, and hyperconjugative stabilizations between... 

Table 3.25 shows how the main NBO descriptors vary in the perp —anti transition of NH2CH2F. As expected, this torsional change leads to strong increases in overlap (from iS ,0 = 0.01 to, Vno = 0.29) and hyperconjugative stabilization (from 0 to 21.7 kcal mol-1), as well as significant population shifts ( 0.07e) fromnN to ocxf. 

The general role of aCH orbitals and hyperconjugative interactions in methyl tilting was suggested much earlier on qualitative grounds H. P. Hamlow, S. Okuda, and N. Nakagawa, Tetrahedron Lett. 1964 (1964), 2553 and note 141. 

The relative strengths of conjugative and hyperconjugative interactions are sharply altered, and general delocalization phenomena become much more pronounced near transition metals, where the abundance of low-lying unfilled valence orbitals provides many new pathways for donor-acceptor stabilization. 

Photoelectron and electron transmission spectroscopy indicate that there is appreciable interaction between the acetylene units of [129] (Houk et al., 1985). Both homoconjugation and hyperconjugation are proposed. Dewar and Holloway (1984) suggest that the through-bond interactions dominate. Similar thermochemical studies to those performed with the triquinacene series were carried out on [129] and some acyclic homoconjugated acetylenes (Scott et al., 1988). From these data it was concluded that decamethyl[5]pericyclyne should be classed as a homoaromatic molecule. As already discussed for the triquinacene series, the species used as non-homoaromatic models (and the calculated compensations for strain energies) may be inappropriate and thus this conclusion should be treated with some caution. Using our probes for homoaromaticity we were not able to obtain any evidence in support of the homoaromaticity of [129] (Williams and Kurtz, unpublished results). 

Finally, Holm and 0gaard Madsen (1992) determined the secondary /3-deuterium KIEs for the addition of /3-deuterated Grignard reagents to unsaturated ketones. Hie authors attributed the small, <5%, KIEs they found in these radical reactions to opposing steric and hyperconjugative effects. 

Some other mechanisms will be discussed in later sections The Grant-Cheney formulation (88) of steric compression effects will appear in the context of y-gauche substituent effects (Section III-C), and hyperconjugative orbital interactions will be cited in interpretations of y-anti substituent (Section III-D) and intramolecular interaction effects (Section IV). 

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

Additional acylation studies were also reported (24), (26). In the first case it is claimed that acylation of thiophene is achieved by means of HC104 and acetic anhydride affording a 65 % yield of 2-acetylthiophene. In the second paper Levine and coworkers reported that while 2,5-dimethylthiophene could be readily acetylated, 2,5-dichlorothiophene acetylated sluggishly. This is, however, readily explained, since the presence of chlorine atoms on the thiophene ring decreased its reactivity in electrophilic substitution reactions. In the case of methyl substitution, however, the 3 and 4 positions of the ring are activated toward electrophilic substitution by the inductive and hyperconjugative effects. Thus 2,5-dimethylthiophene was successfully acylated by the boron fluoride etherate method in high yield with three aliphatic anhydrides. 

Substituted snoutan-9-ones (61a) undergo nucleophilic additions with the same facial selectivity as the corresponding norsnoutanones (61b). However, the selectivity is markedly reduced, apparently owing to electrostatic effects in (61a), and hyperconjugative interactions in (61b). ... 

---