Dihedral angles steric effects

The addition reaction of allylsilane to acetaldehyde with BF3 as the Lewis acid has been modeled computationally.95 The lowest-energy TSs found, which are shown in Figure 9.2, were of the synclinal type, with dihedral angles near 60°. Although the structures are acyclic, there is an apparent electrostatic attraction between the fluorine and the silicon that imparts some cyclic character to the TS. Both anti and syn structures were of comparable energy for the model. However, steric effects that arise by replacement of hydrogen on silicon with methyl are likely to favor the anti TS. 

In contrast, polar and resonance effects must be separated in order to analyze the data for a-substituted arylolefins [ArC(R)=CHR with R H]. Their bromination involves open carbocation intermediates only. Resonance effects cannot be fully developed at the transition states, since the aromatic ring is not in the same plane as that of the developing carbocation, because of steric constraints. Accordingly, application of (33) gives pT < pn. Attenuation of resonance arises mainly from stereochemical factors, at least in the monosubstituted 1,1-diphenylethylene [20] and a-methylstilbene [21] series the pr/pn ratios can be related to the dihedral angle between the substituted phenyl ring and the plane of the ethylenic bond. 

These Xpjr groups represent an especially difficult problem because their delocalized electrical effect depends on the steric effect when they are bonded to planar jr-bonded skeletal groups, Gp7r. An approach to the problem has been developed45,46. The electrical effect parameters are a function of the dihedral angle formed by Xp3r and Gpn. The relationship generally used has the form ... 

In the case of planar jr-bonded groups, the maximum and minimum values of the steric parameter are available from the van der Waals radii (Figure 2). Both the steric effect and the delocahzed electrical effect are a function of the dihedral angle when this type of group is bonded to an sp hybridized carbon atom of a skeletal group . ... 

C-H bond oxygen insertion, 1163 configuration retention, 1163 epoxidation, 1144-50 hydroperoxy anion transfer, 382 Steric effects hydrogen dioxide, 96-7 peroxide dihedral angle, 101, 177 Steric strain... 

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