Allylamines nitrogen nucleophiles

Termination by external nitrogen nucleophiles has been investigated for various systems (cf. Ref. [53]). AUenes, which are excellent relays for cascade reactions, give rise to the formation of Tr-aUylpaUadium complexes. The latter can be reacted in a straightforward manner with amines to yield highly functionalized allylamines (Scheme 30, Eqs. 1 and... 

This methodology was extended by Cardillo et al. to the synthesis of chiral a-benzylamino- S,y-unsaturated acids, starting from a-bromo-a,l -unsaturated chlorides. The treatment of these latter compounds with (i )-pantolactone in the presence of triethylamine (TEA) allowed the in situ formation of the deconjugated ketenes and their direct transformation into the corresponding chiral esters. The substitution of bromine with benzylamine, followed by add hydrolysis, produced enantiomerically enriched a-benzylamino-/ ,y-unsaturated acids (Scheme 1.14). The displacement of the bromine with other nitrogen nucleophiles, such as / -methoxybenzylamine and allylamine, also occurred with good yields with complete diastereoselectivity. 

Early on, Heck and co-workers found that intra- and intermolecular coupling reactions of haloalkenes with alkenes in the presence of secondary amines gave allylamines.t t Apparently, an intermediate 7r-allylpalladium complex is formed by rearranganent of the (7-homoallylpalladium intermediate (see above, B.ii) and in turn attacked by the nitrogen nucleophile. Excellent yields of tertiary aUylamines are obtained in this three-component coupling (Scheme As far as the outcome is concerned, analogous inter-intra- as well as fully intramolecular processes have been estabhshed (Scheme 30 see Table... 

Allylamines in which the nitrogen has been made less nucleophilic by appropriate substitution do not undergo ylide formation and are amenable to cyclopropanation. This is the case in allylbis(trimethylsilyl)amines and A-acylallylamines , e.g. formation of cyclopropanes 24 and 25 a, b. 

As illustrated in Scheme 10.8, the amino group-terminated polypropylene is probably obtained through a special chain transfer mechanism that may involve a dormant species (iii) formed after insertion of the alkylaluminum-treated allylamine. The nitrogen atom of the inserted masked allylamine is located near the Zr cation and results in a stable complex (iii), to which nucleophilic attack from A1(CH3 )3 can occur at the chain end to produce a polymeric intermediate (iv). With HCl treatment during workup, this intermediate (iv) is converted into iPP-NH2 (v). ... 

The allylic nitrogen derivatives, such as allylic ammonium salts, tosylimides, and nitro compounds, react with Pd(0) species under mild reaction conditions to form rr-allylpalla-dium intermediates, which undergo coupling reaction with various nucleophiles to give allylated nucleophiles. Carbon monoxide reacts with the 7r-allylpalladium species derived from allylamines to give /3,y-unsaturated amides. 

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