Photocatalytic synthesis of homoallylic amines <i>via</i> nucleophilic addition of nickel allyl complexes to imines

Homoallylic amines can be found in pharmaceutically interesting molecules and are versatile building blocks for total synthesis. Herein, we present a three-component coupling reaction of an aldehyde, an aniline and an allylic carbonate or allene to yield branched homoallylic amines in good yields and diastereoselectivity. Our straightforward protocol proceeds <i>via</i> the addition of an allyl nickel species to an <i>in situ</i> formed imine and represents the first photocatalytic realization of the classic approach of allyl metal addition to imines. Next to some follow-up transformations, a detailed reaction mechanism backed by experimental observations is presented.