Allyl chloride reactions with nitrogen nucleophiles

Nitrogen compounds serve as reactive nucleophiles toward rr-allylpalladium complexes (Scheme 1). Diethylamine is allylated with allyl alcohol.Allylic chlorides react with amines without a Pd catalyst, but the reaction is accelerated with such a catalyst. For example, in the Pd-catalyzed reaction of l-acetoxy-4-chloro-2-butene with diethyl amine at 25 °C, only the allylic chloride is displaced without attacking the allylic acetatoxy moiety. The uncatalyzed reaction proceeds at 80 The secondary amine is obtained without... 

A combination of bis(iridiumcyclooctadienyl chloride) [Ir(COD)Cl]2, a chiral phosphor-amidite ligand, and DBU (1) as a base in THF effects the iridium (I) catalysed intermolec-ular allylic amidation of ethyl allyl carbonates with soft nitrogen nucleophiles under completely salt-free conditions [70]. The reaction is quite general, accommodating a wide variety of substrates and nucleophiles, and proceeds with excellent regio- and enantios-electivities to afford the branched Ai-protected allyl amines. 

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