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Updated: Jan 17, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Ti-Catalyzed Oxidative Amination Using Anilines
Steven K Butler1, Ethan P Ashbrook1, Michael R Harris1
1Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
Abstract:
In this report, Ti-catalyzed transfer hydrogenation from anilines to alkynes is leveraged to generate nitrenes from anilines in the Ti-catalyzed [2+2+1] synthesis of N-aryl pyrroles. While there are myriad methods for accessing nitrene reactive intermediates in chemical synthesis, methods for the direct transformation of amines into nitrene equivalents are uncommon. This transfer hydrogenation-coupled [2+2+1] pyrrole synthesis is catalyzed by a recently-reported bis(phenoxide) Ti complex, (TPO)Ti(NMe2)2 (TPO = (3,3″-di-tert-butyl-5,5″-dimethyl-[1,1':2',1″-terphenyl]-2,2″-bis(olate)). Preliminary mechanistic insight indicates that a balance of the competition between alkyne insertion into titanacycle Ti-C bonds versus Ti-C aminolysis at several points along the catalytic cycle is critical for productive catalysis over unwanted side reactions such as alkyne hydroamination or alkyne cyclotrimerization.
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