Photochemical Organocatalytic Regio‐ and Enantioselective Conjugate Addition of Allyl Groups to Enals

We report the first catalytic enantioselective conjugate addition of allyl groups to α,β‐unsaturated aldehydes. The chemistry exploits the visible‐light‐excitation of chiral iminium ions to activate allyl silanes towards the formation of allylic radicals, which are then intercepted stereoselectively. The underlying radical mechanism of this process overcomes the poor regio‐ and chemoselectivity that traditionally affects the conjugate allylation of enals proceeding via polar pathways. We also demonstrate how this organocatalytic strategy could selectively install a valuable prenyl fragment at the β‐carbon of enals.