Decarboxylative Formylation of Aryl Halides with Glyoxylic Acid by Palladium Catalysis under Oxygen

Abstract

A new free radical/palladium cooperative catalyzed formylation of aryl halides with glyoxylic acid as the formyl source under oxygen conditions has been developed. Various aromatic and heteroaromatic aldehydes were produced in medium to good yields.

Key words

aryl halide - reductive carbonylation - aldehydes - palladium catalysis - synthetic methods

• References and Notes

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• 17 Typical Procedure: Iodobenzene (1; 0.204 g, 1.0 mmol), PdCl₂ (PPh₃)₂ (0.021 g, 0.03 mmol), glyoxylic acid monohydrate (0.552 g, 6.0 mmol) and AIBN (0.082 g, 0.05 mmol) were transferred into a 50 mL Schlenk tube that was filled with oxygen. After DMF (2.0 mL) and Et₃N (0.606 g, 6.0 mmol) were added successively, the tube was sealed and the mixture was stirred at 110 °C for 4 h. Upon completion of the reaction, the mixture was poured into saturated aqueous NaCl solution (25 mL) and extracted with CH₂Cl₂ (4 × 15 mL). The combined organic layers were washed with brine (4 × 20 mL), dried over MgSO₄, filtered, and concentrated. The residue was purified by column chroma­tography on silica gel (PE/EtOAc, 25:1) to afford the corresponding product (0.074 g, 70%) as a colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 10.01 (s, 1 H), 7.89–7.86 (m, 2 H), 7.65–7.65 (m, 1 H), 7.53 (t, J = 7.6, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 192.48, 136.37, 134.50, 129.77, 129.02.