Catalytic C(sp(3) )-H Arylation of Free Primary Amines with an exo Directing Group Generated In Situ

Yan Xu; Michael C Young; Chengpeng Wang; David M Magness; Guangbin Dong

doi:10.1002/anie.201604268

Catalytic C(sp(3) )-H Arylation of Free Primary Amines with an exo Directing Group Generated In Situ

Angew Chem Int Ed Engl. 2016 Jul 25;55(31):9084-7. doi: 10.1002/anie.201604268. Epub 2016 Jun 8.

Authors

Yan Xu¹, Michael C Young¹, Chengpeng Wang¹, David M Magness¹, Guangbin Dong²

Affiliations

¹ Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
² Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA. [email protected].

PMID: 27276342
DOI: 10.1002/anie.201604268

Abstract

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.

Keywords: C−H activation; arylation; directing groups; palladium catalysis; primary amines.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.