Mahesh P Paudyal1, Adeniyi Michael Adebesin1, Scott R Burt2, Daniel H Ess2, Zhiwei Ma3, László Kürti3, John R Falck4. 1. Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, TX 75390, USA. 2. Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602, USA. 3. Department of Chemistry, Rice University, BioScience Research Collaborative, Houston, TX 77005, USA. 4. Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, TX 75390, USA. j.falck@utsouthwestern.edu.
Abstract
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.
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 n class="Chemical">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.
Authors: Kumiko Yamamoto; Jiakun Li; Jeffrey A O Garber; Julian D Rolfes; Gregory B Boursalian; Jannik C Borghs; Christophe Genicot; Jérôme Jacq; Maurice van Gastel; Frank Neese; Tobias Ritter Journal: Nature Date: 2018-02-21 Impact factor: 49.962