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Updated: May 21, 2025

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Trifunctionalization of Iodoarenes via Sequence-Controlled Double Ortho C─H Acylations by Palladium/Norbornene
Yong Xu1, Lifeng Wang1, Aohua Yang1
1Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an, China.
Abstract:
Herein we report a novel palladium/norbornene-catalyzed trifunctionalization reaction of ortho-unsubstituted iodoarenes by incorporating two distinct acyl groups at their ortho C─H positions and replacing the ipso-iodide with an alkenyl or aryl group. Notably, this transformation was enabled by the alkyl/aryl mixed anhydrides, which were utilized as dual acylation reagents by abstracting their central oxygen atom with electrophilic 2-chloro-4,6-dimethoxy-1,3,5-triazine. Mechanistic studies revealed that the alkyl-acyl unit of such an anhydride was employed for the first C─H alkyl-acylation, and in situ released aryl carboxylate anion was then rapidly activated with triazine chloride to provide an aryl-acyl electrophile for the second C─H acylation, thus enabling the trifunctionalization of iodoarenes by termination with an intermolecular Heck or intramolecular arylation reaction. In addition, the synthetic utility of this method is exemplified by the selective manipulation of carbonyl groups of the products.
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