Aldimines homoallylamines from

Asymmetric allylation of aldimine providing chiral homoallylamines is accomplished by using 5 mol % of 7r-allylpalladium chloride dimer derived from (75)-/3-(-)pinene (Scheme 29)P The pinene moiety serves not only as a chiral auxiliary but also as a dummy 7r-allyl group of unsymmetrical bis-7r-allylpalladium intermediate. The asym-metric induction is successful for aldimines derived from alkylamines (benzy-lamine, p-methoxybenzylamine, and isopropylamine) however, no asymmetric induction is observed for aldimines of aniline. 

When a disubstituted imine (19a-d) is employed instead of the trisubstituted imine, in addition to the homoallylamine (20) also the hydrodimer (21) of the imine, i.e., the dimer of the postulated a-aminobenzyl radical, is isolated (Figure 30) [214, 45]. The observation that the hydrodimer is produced only from the disubstituted and not from the trisubstituted imine parallels the electrochemical reduction which affords hydrodimers from aldimines [215] but not from ketimines [215, 216]. 

Aldimines, R CH=NR, react with allyltrimethylsilane in the presence of w-butyl-ammonium fluoride to give homoallylamines, R CH(NHR )CH2CH=CH2 fluoride-triggered autocatalysis is again proposed. Allylation of imines has been achieved via in situ formation of an A-tosyliminium species from aldehydes or ketones." ... 

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