Iridium complex-catalyzed allylic amination of allylic carbonates was studied. The solvent strongly
affected the catalytic activity. The use of a polar solvent such as EtOH is essential for obtaining the products
in high yield. The reaction of (E)-3-substituted-2-propenyl carbonate and 1-substituted-2-propenyl carbonate
with pyrrolidine in the presence of a catalytic amount of [Ir(COD)Cl]2 and P(OPh)3 (P/Ir = 2) gave a branch
amine with up to 99% selectivity. Both secondary and primary amines could be used for this reaction. When
a primary amine was used, selective monoallylation occurred. No diallylation product was obtained. The reaction
of 1,1-disubstituted-2-propenyl acetate with amines exclusively gave an α,α-disubstituted allylic amine. This
reaction provides an alternative route to the addition of an organometallic reagent to ketimines for the preparation
of such amines. The reaction of (Z)-3-substituted-2-propenyl carbonate with amines gave (Z)-linear amines
with up to 100% selectivity. In all cases, no (E)-linear amine was obtained. The selectivities described here
have not been achieved in similar palladium complex-catalyzed reactions.