Regio‐, Diastereo‐, and Enantioselective Decarboxylative Hydroaminoalkylation of Dienol Ethers Enabled by Dual Palladium/Photoredox Catalysis

Abstract Intermolecular photocatalytic hydroaminoalkylation (HAA) of alkenes have emerged as a powerful method for the construction of alkyl amines. Although there are some studies aiming at stereoselective photocatalytic HAA reactions, the alkenes are limited to electrophilic alkenes. Herein, we report a highly regio‐, diastereo‐, and enantioselective HAA of electron‐rich dienol ethers and α‐amino radicals derived from α‐amino acids using a unified photoredox and palladium catalytic system. This decarboxylative 1,2‐Markovnikov addition enables the construction of vicinal amino tertiary ethers with high levels of regio‐ (up to >19 : 1 rr), diastereo‐ (up to >19 : 1 dr), and enantioselectivity control (up to >99 % ee). Mechanistic studies support a reversible hydropalladation as a key step.