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Updated: Aug 18, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Catalytic intermolecular ortho-arylation of phenols
Robin B Bedford1, Michael E Limmert
1School of Chemistry, University of Exeter, Exeter EX4 4QD, UK. r.bedford@ex.ac.uk
Abstract:
The use of rhodium catalysts such as [RhCl(PPh3)3] or [[RhCl(COD)]2] with PiPr2(OAr) or P(NMe2)3 co-catalysts allows the ortho-selective intermolecular arylation of phenols. The reaction proceeds via orthometalation of P-OAr groups and then transesterification liberates the product phenol. When 2-substituted phenols are used as substrates, [RhCl(PPh3)3]/iPr2(OAr) mixtures are typically the catalysts of choice, whereas for substrates without 2-substitution [[RhCl(COD)]2]/P(NMe2)3 mixtures tend to give better results.
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