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Updated: Aug 5, 2025

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Manganese(I) Catalyzed ortho C-H Allylation of Benzoic Acids
Jonas F Goebel1, Johanna Stemmer1, Florian Belitz1
1Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
Abstract:
The 3d-metal catalyst Mn(CO)5 Br was found to efficiently promote ortho C-H allylations of arenecarboxylates in the presence of neocuproine as the ligand. Despite the simplicity of directing group and catalyst system, the selectivity goes well beyond the state-of-the-art in that mono-allylated products are obtained exclusively with high selectivities for the least hindered ortho-position. The directing group can optionally be removed by in situ decarboxylation, opening up a regioselective entry to allyl arenes. The preparative utility of the process and its othogonality to other approaches was demonstrated by 44 products with otherwise hard-to-access substitution patterns, including 3-bromo-allylbenzene, 3-allylbenzofuran, or 5-allyl-2-methylnitrobenzene.
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