Catalytic C(sp(3) )-H Arylation of Free Primary Amines with an exo Directing Group Generated In Situ.
Herein, we report the palladium-catalyzed direct arylation of unactivated aliphatic C-H bonds in free primary amines. This method takes advantage of an exo-imine-type directing group (DG) that can be generated and removed in situ. A range of unprotected aliphatic amines are suitable substrates, undergoing site-selective arylation at the γ-position. Methyl as well as cyclic and acyclic methylene groups can be activated. Furthermore, when aniline-derived substrates were used, preliminary success with δ-C-H arylation was achieved. The feasibility of using the DG component in a catalytic fashion was also demonstrated.
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
Yan
Y
Xu
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
Michael C
MC
Young
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
Chengpeng
C
Wang
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
David M
DM
Magness
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA. gbdong@cm.utexas.edu.
Guangbin
G
Dong
C−H activation; arylation; directing groups; palladium catalysis; primary amines