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A divergent synthesis of ortho‐anisidines was achieved by controlling Cu‐catalyzed [1,3]‐methoxy rearrangement. The reactions of N‐alkoxyanilines having an electron‐donating group (EDG), such as an alkyl or anisyl group, at the ortho position and a pivaloyl group on the nitrogen atom in the presence of catalytic amounts of IPrMeCuCl and AgNTf2 afforded the corresponding 6‐substituted 2‐anisidines...
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