Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd–PHOX Catalyst

• DOI: 10.1021/jacs.7b03480
• Publication Date: 2017-04-28T16:37:18Z
• Authors: Nathan J. Adamson; Ethan Hull; Steven J. Malcolmson
• Keywords: Alkadienes; Allyl Compounds; Molecular Structure; Organometallic Compounds; Stereoisomerism; Amines; Oxazoles; 01 natural sciences; Catalysis; Palladium; 0104 chemical sciences

We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.