Transition-Metal-Free Hunsdiecker Reaction of Electron-Rich Arenecarboxylic Acids and Aryl Aldehydes in Water

Abstract

An I₂O₅-mediated decarboxylative and decarbonylative bromination/iodination of electron-rich arenecarboxylic acids and aryl aldehydes by using KBr/KI as the halogen source in water has been developed. This scalable, low-cost, and transition-metal-free halogenation allows convenient access to aryl bromide and iodide under mild conditions.

Key words

I₂O₅-mediated - decarboxylative - decarbonylative - bromination - iodination - arenecarboxylic acids - aryl aldehydes

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• 16 Representative Procedure for Decarboxylative Iodination A mixture of aryl carboxylic acids or aldehydes (0.2 mmol, 1 equiv), KI (0.5 mmol, 2.5 equiv), I₂O₅ (0.4 mmol, 2 equiv), and H₂O (2 mL) was heated in an open flask at 50 °C for 22 h. After the reaction finished, a sat. aq solution of Na₂S₂O₃ (5 mL) was added into the mixture, then it was abstracted by CH₂Cl₂ (3 × 5 mL). The organic layer was dried with anhydrous Na₂SO₄, the filtrate was evaporated under vacuum and purified by column chromatography to afford the desired product. Representative Procedure for Decarboxylative Bromination A mixture of aryl carboxylic acids or aldehydes (0.2 mmol, 1 equiv), KBr (0.5 mmol, 2.5 equiv), I₂O₅ (0.4 mmol, 2 equiv), and H₂O (2 mL) was heated in an open flask at 25 °C for 22 h. After the reaction finished, a sat. aq solution of Na₂S₂O₃ (5 mL) was added into the mixture, then it was abstracted by CH₂Cl₂ (3 × 5 mL). The organic layer was dried with anhydrous Na₂SO₄, the filtrate was evaporated under vacuum and purified by column chromatography to afford the desired product.