title: Selective Radical-Radical Cross-Couplings: Design of a Formal β-Mannich Reaction.
abstract: A direct β-coupling of cyclic ketones with imines has been accomplished via the synergistic combination of photoredox catalysis and organocatalysis. Transient β-enaminyl radicals derived from ketones via enamine and oxidative photoredox catalysis readily combine with persistent α-amino radicals in a highly selective hetero radical-radical coupling. This novel pathway to γ-aminoketones is predicated upon the use of DABCO as both a base and an electron transfer agent. This protocol also formally allows for the direct synthesis of β-Mannich products via a chemoselective three-component coupling of aryl aldehydes, amines, and ketones.
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: Jenna L
authors.initials: JL
authors.lastname: Jeffrey
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: Filip R
authors.initials: FR
authors.lastname: Petronijević
authors.affiliation: Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
authors.forename: David W C
authors.initials: DW
authors.lastname: MacMillan
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods*; D004583:Electrons; D005609:Free Radicals; D007097:Imines / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010777:Photochemistry / Q000379:methods; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000588:Amines; D005609:Free Radicals; D007097:Imines; D007659:Ketones; D010100:Oxygen