Catalysis

Photochemistry

Alkyl

Markovnikov's rule

Medicinal chemistry

Physics

Organic chemistry

Hydroamination

Amination

Astronomy

Amine gas treating

Primary (astronomy)

Regioselectivity

Chemistry

Aryl

Olefin fiber

Photocatalysis

Journal of the American Chemical Society

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.

Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines