Allylic amine isomerization kinetics

Allylic amide isomerization, 117 Allylic amine isomerization ab initio calculations, 110 catalytic cycle, 104 cobalt-catalyzed, 98 double-bond migration, 104 isotope-labeling experiments, 103 kinetics, 103 mechanism, 103 model system, 110 NMR study, 104 rhodium-catalyzed, 9, 98 Allylnickel halides, 170 Allylpalladium intermediates, 193 Allylsilane protodesilylation, 305 Aluminum, chiral catalysts, 216, 234, 310 Amide dimers, NMR spectra, 282, 284 Amines ... 

Studies on the origin of die regioselectivity of these reactions revealed that attack by amines occurred at the more-substituted position, but isomerization of the kinetic branched product to the thermodynamic linear product occurred faster than the catalytic process. As a result, the linear isomer was observed as the final reaction product. However, isomerization of the products formed by reactions of aziridines, hydroxylamines, and hydrazone deriviatives was slower than the catalytic substitution process, and these different relative rates allowed isolation of the branched substitution products. The isomerization process presumably occurs by protonation of the amine to form an ammonium salt that undergoes oxidative addition to palladium, as was observed in the initial allyUc substitution processes that involved allylic ammonium salts as electrophile. Thus, addition of a strong, non-nucleophihc base to the reactions of amine nucleophiles allowed isolation of the branched kinetic product. ... 

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