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Updated: Sep 23, 2025

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Insight into trifluoromethylation - experimental electron density for Togni reagent I
1Institute of Inorganic Chemistry, RWTH Aachen University Landoltweg 1 52074 Aachen Germany ullrich.englert@ac.rwth-aachen.de.
Abstract:
3,3-Dimethyl-1-(trifluoromethyl)-1,3-dihydro-1-λ3,2-benziodoxole represents a popular reagent for trifluoromethylation. The σ hole on the hypervalent iodine atom in this "Togni reagent" is crucial for adduct formation between the reagent and a nucleophilic substrate. The electronic situation may be probed by high resolution X-ray diffraction: the experimental charge density thus derived shows that the short intermolecular contact of 3.0 Å between the iodine and a neighbouring oxygen atom is associated with a local charge depletion on the heavy halogen in the direction of the nucleophile and visible polarization of the O valence shell towards the iodine atom. In agreement with the expectation for λ3-iodanes, the intermolecular O⋯I-Caryl halogen bond deviates significantly from linearity.
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