title: Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines.
abstract: The intermolecular hydroamination of unactivated alkenes with simple dialkyl amines remains an unsolved problem in organic synthesis. We report a catalytic protocol for efficient additions of cyclic and acyclic secondary alkyl amines to a wide range of alkyl olefins with complete anti-Markovnikov regioselectivity. In this process, carbon-nitrogen bond formation proceeds through a key aminium radical cation intermediate that is generated via electron transfer between an excited-state iridium photocatalyst and an amine substrate. These reactions are redox-neutral and completely atom-economical, exhibit broad functional group tolerance, and occur readily at room temperature under visible light irradiation. Certain tertiary amine products generated through this method are formally endergonic relative to their constituent olefin and amine starting materials and thus are not accessible via direct coupling with conventional ground-state catalysts.
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
authors.forename: Andrew J
authors.identifier: 0000-0002-8110-3540
authors.initials: AJ
authors.lastname: Musacchio
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
authors.forename: Brendan C
authors.identifier: 0000-0002-0559-9919
authors.initials: BC
authors.lastname: Lainhart
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
authors.forename: Xin
authors.identifier: 0000-0001-5019-5545
authors.initials: X
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
authors.forename: Saeed G
authors.initials: SG
authors.lastname: Naguib
authors.affiliation: Discovery Chemistry, Bristol-Myers Squibb Co., Princeton, NJ 08543, USA.
authors.forename: Trevor C
authors.identifier: 0000-0003-3070-6373
authors.initials: TC
authors.lastname: Sherwood
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA. rknowles@princeton.edu.
authors.forename: Robert R
authors.identifier: 0000-0003-1044-4900
authors.initials: RR
authors.lastname: Knowles