Journal of Organic Chemistry 2015-08-21

Steric-Hindrance-Induced Regio- and Chemoselective Oxidation of Aromatic Amines.

Vilas Venunath Patil, Ganapati Subray Shankarling

Index: J. Org. Chem. 80(16) , 7876-83, (2015)

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Abstract

Unusual regio- and chemoselective oxidation of aromatic amines hindered with ortho substituents (except -NH2, -NHCH3, and -OH) to the corresponding nitro compounds is described by use of nonanebis(peroxoic acid). The mechanistic investigation for selective oxidation of amines ortho-substituted with -NH2 or -OH showed the involvement of H-bonding between the ortho hydrogen of the adjacent -XH group (where X = NH, NR, or O) and an oxygen atom from the diperoxy acid. Various mono- and diamines are oxidized into corresponding mononitro derivatives in high yield and purity without employing any protection strategies. The protocol was also found to successful on the gram scale.