Selective Oxidation of Styrene Derivatives to Ketones over Palladium(0)/Carbon with Hydrogen Peroxide as the Sole Oxidant

Abstract

Pd⁰/C catalyst exhibited excellent catalytic activity in the Wacker oxidation of styrene derivatives to corresponding ketones with hydrogen peroxide as a clean oxidant. Compared with the conventional Wacker system, the newly developed method offers a cost-efficient and environmentally friendly option without the use of a copper salt as a co-catalyst.

Key words

Wacker oxidation - palladium catalysis - heterogeneous catalysis - hydrogen peroxide - styrenes - ketones

• References and Notes

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• 21 Wacker Oxidation of Olefins; General Procedure 5 wt% Pd⁰/C (0.05 mmol) and 70 wt% H₂SO₄ (0.2 mmol) were added to a solution of the appropriate styrene (1 mmol) in MeCN (5 mL), and the mixture was stirred for about 15 min at r.t. Then, 30 wt% H₂O₂ (6 mmol) was added dropwise, and the mixture was heated at 65 °C until the reaction was complete (TLC). The Pd⁰/C was removed by centrifugation and the remaining mixture was partitioned between H₂O and EtOAc. The layers were separated, and the organic layer was washed with H₂O, dried (Na₂SO₄), filtered, and concentrated under reduced pressure. The crude residue was purified by column chromatography. Acetophenone (Table 2, Entry 16) Light-yellow liquid; yield: 1.03 g (90%). ¹H NMR (300 MHz, CDCl₃): δ = 7.96 (d, J = 7.1 Hz, 2 H), 7.57 (t, J = 7.3 Hz, 1 H), 7.47 (t, J = 7.4 Hz, 2 H), 2.61 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 198.1, 136.9, 133.0, 128.4, 128.2, 26.5.