Pd-Catalyzed asymmetric allylic amination with isatin using a P,olefin-type chiral ligand with C–N bond axial chirality

In this study, we implemented the P,olefin-type chiral ligand (a<i>R</i>)-(-)-<b>6</b>, which contains a cyclohexyl group and a cinnamoyl group on the nitrogen atom, in the Pd-catalyzed asymmetric allylic amination of allylic esters with isatin derivatives <b>11</b> as nucleophiles. The reaction proceeds efficiently, yielding the products (<i>S</i>)-<b>13</b> with good-to-high enantioselectivity. A scale-up reaction was also successfully conducted at a 1 mmol scale. Additionally, when malononitrile was added to the resulting product (<i>S</i>)-<b>13a</b> in the presence of FeCl₃ as the catalyst, the corresponding malononitrile derivative (<i>S</i>)-<b>16</b> was obtained without any loss in optical purity.