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Updated: Mar 2, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Chemoselective Copper-Catalyzed Ullmann-Type Coupling of Oxazolidinones with Bromoiodoarenes
Sean M Kelly1, Chong Han1, Laura Tung1
1Department of Small Molecule Process Chemistry, Genentech, Inc. , South San Francisco, California 94080, United States.
Abstract:
We describe the highly selective copper-catalyzed Ullmann-type coupling of bromoiodoarenes with oxazolidinones. 3,4,7,8-Tetramethyl-1,10-phenanthroline (Me4Phen) was identified as an optimal ligand promoting the desired C-N bond formation, while minimizing the competitive bromo-iodo exchange pathway that leads to formation of iodo-substituted and bis-coupled side products. The developed method is highly selective with a >98:2 ratio of the bromo- vs iodo-substituted compounds obtained in the isolated products.
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