Olefinic group, allylic effect

Three different principles of selectivity are required to achieve this result. First, the difference in rate of epoxidation by the catalyst of a disubstituted versus a monosubstituted olefin must be such that the propenyl group is epoxidized in complete preference to the vinyl group. The effect of this selectivity is to reduce the choice of olefinic faces to four of the two propenyl groups. Second, the inherent enantiofacial selectivity of the catalyst as represented in Figure 6A.1 will narrow the choice of propenyl faces from four to two. Finally, the steric factor responsible for kinetic resolution of 1-substituted allylic alcohols (Fig. 6A.2) will determine the final choice between the propenyl groups in the enantiomers of 80. The net result is the formation of epoxy alcohol 81 and enrichment of the unreacted allylic alcohol in the (35)-enantiomer. 

Due to the chelating effect of the amino group, allylic amines readily undergo nucleophilic addition reaction on their double bond. For example, carbopallada-tion of allyl-dimethylamine with malonates readily yields a chelating complex. Subsequent olefin insertion of methyl vinyl ketone into this complex gives co-amino enones23) (Scheme 17). An interesting application of the facile earbopalladation de-... 

In their analysis of H-NMR spectra of various end functionalised polyisobutylenes (PIB). Si and Kennedy [50] covered inductive effects (due to ert-chlorine-ended PIB), magnetic anisotropic effects (due to olefin groups and phenyl rings) and allylic coupling (due to olefinic end-groups) ... 

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