Dirhodium-catalyzed C-H arene amination using hydroxylamines.
Primary and N-alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals, and functional materials, as well as in bioactive natural products. However, there is a dearth of generally applicable methods for the direct replacement of aryl hydrogens with NH2/NH(alkyl) moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N-alkyl arylamines using NH2/NH(alkyl)-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO2O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N-heterocycles.
Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, TX 75390, USA.
Mahesh P
MP
Paudyal
Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, TX 75390, USA.
Adeniyi Michael
AM
Adebesin
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602, USA.
Scott R
SR
Burt
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602, USA.
Daniel H
DH
Ess
Department of Chemistry, Rice University, BioScience Research Collaborative, Houston, TX 77005, USA.
Zhiwei
Z
Ma
Department of Chemistry, Rice University, BioScience Research Collaborative, Houston, TX 77005, USA.
László
L
Kürti
Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, TX 75390, USA. j.falck@utsouthwestern.edu.
John R
JR
Falck