Allylic rearrangement

Organic chemistry

Amination

Combinatorial chemistry

Palladium

Catalysis

Medicinal chemistry

Intermolecular force

Chemistry

Bromide

Molecule

Alkyl

Aryl

Science

Aliphatic allylic amines are found in a great variety of complex and biorelevant molecules. The direct allylic C-H amination of alkenes serves as the most straightforward method toward these motifs. However, use of widely available internal alkenes with aliphatic amines in this transformation remains a synthetic challenge. In particular, palladium catalysis faces the twin challenges of inefficient coordination of Pd(II) to internal alkenes but excessively tight and therefore inhibitory coordination of Pd(II) by basic aliphatic amines. We report a general solution to these problems. The developed protocol, in contrast to a classical Pd(II/0) scenario, operates through a blue light-induced Pd(0/I/II) manifold with mild aryl bromide oxidant. This open-shell approach also enables enantio- and diastereoselective allylic C-H amination.

Asymmetric intermolecular allylic C–H amination of alkenes with aliphatic amines