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Updated: Jan 18, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Photomediated C-H trifluoromethoxylations enabled by bis(trifluoromethyl)peroxide
Kamar Shakeri1, Merlin Kleoff2, Paul Golz2
1Freie Universität Berlin, Institute of Chemistry and Biochemistry, Organic Chemistry Takustr. 3 14195 Berlin Germany mathias.christmann@fu-berlin.de.
Abstract:
We describe a photomediated protocol for the trifluoromethoxylation of benzylic, aldehydic, and non-activated C-H bonds, using bis(trifluoromethyl)peroxide (BTMP, (F3CO)2) as the key reagent. Under catalyst-free conditions in acetone, this reaction proceeds with selective functionalization of benzylic methylene groups. Furthermore, by using tetrabutylammonium decatungstate as a photocatalyst, the scope extends to include both non-activated methylene C(sp3)-H and formyl C(sp2)-H bonds. The methodology was successfully applied to 24 examples including odorants, pharmaceuticals, and natural products and was demonstrated on gram scale. Finally, by using [13C]-BTMP, the corresponding trifluoromethoxy groups can be site-specifically labeled with 13C.
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