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Dirhodium-catalyzed C-H arene amination using hydroxylamines.

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.

SUBMITTER: Paudyal MP

PROVIDER: S-EPMC5040325 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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Dirhodium-catalyzed C-H arene amination using hydroxylamines.

Paudyal Mahesh P MP Adebesin Adeniyi Michael AM Burt Scott R SR Ess Daniel H DH Ma Zhiwei Z Kürti László L Falck John R JR

Science (New York, N.Y.) 20160901 6304

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 ...[more]

PMID: 27609890

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