Open AccessAnti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines
Author(s) -
David C. Miller,
Jacob M. Ganley,
Andrew J. Musacchio,
Trevor C. Sherwood,
William R. Ewing,
Robert R. Knowles
Publication year - 2019
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.9b08746
Subject(s) - chemistry , markovnikov's rule , hydroamination , alkyl , olefin fiber , primary (astronomy) , amination , aryl , amine gas treating , organic chemistry , photocatalysis , photochemistry , medicinal chemistry , catalysis , regioselectivity , physics , astronomy
We report here a photocatalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary alkyl amines to selectively furnish secondary amine products. These reactions proceed through aminium radical cation (ARC) intermediates and occur at room temperature under visible light irradiation in the presence of an iridium photocatalyst and an aryl thiol hydrogen atom donor. Despite the presence of excess olefin, high selectivities are observed for secondary over tertiary amine products, even though the secondary amines are established substrates for ARC-based olefin amination under similar conditions.