Dirhodium-catalyzed C-H arene amination using hydroxylamines

作者：Paudyal Mahesh P; Adebesin Adeniyi Michael; Burt Scott R; Ess Daniel H; Ma Zhiwei; Kurti Laszlo; Falck John R^*

来源：Science, 2016, 353(6304): 1144-1147.

DOI：10.1126/science.aaf8713

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.

• 出版日期2016-9-9