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Updated: Dec 13, 2025

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Iodane-Guided ortho C-H Allylation
Wei W Chen1,2, Anton Cunillera1, Dandan Chen3,4
1Dept. of Biological Chemistry, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Institute of Advanced Chemistry of Catalonia (IQAC-CSIC), c/Jordi Girona 18-26, 08034, Barcelona, Spain.
Abstract:
A metal-free C-H allylation strategy is described to access diverse functionalized ortho-allyl-iodoarenes. The method employs hypervalent (diacetoxy)iodoarenes and proceeds through the iodane-guided "iodonio-Claisen" allyl transfer. The use of allylsilanes bearing electron-withdrawing functional groups unlocks the functionalization of a broad range of substrates, including electron-neutral and electron-poor rings. The resulting ortho-allylated iodoarenes are versatile building blocks, with examples of downstream transformation including a concise synthesis of the experimental antimitotic core of Dosabulin. DFT calculations shed additional light on the reaction mechanism, with notable aspects including the aromatic character of the transition-state structure for the [3,3] sigmatropic rearrangement, as well as the highly stereoconvergent nature of the trans-product formation.
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