Palladium-Catalyzed Carbonylative Cyclization of β-Bromo-α,β-unsaturated Carboxylic Acids Leading to Maleic Anhydrides

Abstract

β-Bromo-α,β-unsaturated carboxylic acids are carbonylatively cyclized under carbon monoxide pressure in acetic acid in the presence of a catalytic amount of a palladium catalyst along with a base to give the corresponding maleic anhydrides in high yields.

Key words

carbonylation - cyclization - heterocycles - homogeneous catalysis - palladium

• References and Notes

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• 13 Yields of Several β-Bromo-α,β-unsaturated Carboxylic Acids from the Corresponding β-Bromo-α,β-unsaturated Aldehydes and Spectroscopic DataCompound 1c: 250 mg (89%); solid; mp 136–137 °C. ¹H NMR (400 MHz, CDCl₃): δ = 1.89–2.02 (m, 2 H), 2.45–2.54 (m, 1 H), 2.76–2.83 (m, 3 H), 2.87–2.95 (m, 1 H), 7.20–7.25 (m, 3 H), 7.30–7.34 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 30.98, 36.37, 38.71, 39.04, 126.88, 126.95, 128.85, 129.22, 129.75, 144.59, 171.93.Compound 1f: 246 mg (85%); solid; mp 116–117 °C. ¹H NMR (400 MHz, CDCl₃): δ = 1.33–1.38 (m, 12 H), 1.55–1.61 (m, 2 H), 1.72–1.78 (m, 2 H), 2.44–2.48 (m, 2 H), 2.58–2.62 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 22.47, 22.82, 24.34, 24.39, 24.44, 24.58, 25.72, 25.98, 28.66, 33.91, 128.44, 134.84, 173.57.Compound 1g: 127 mg (50%); solid; mp 123–124 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.72–2.76 (m, 2 H), 2.86–2.90 (m, 2 H), 7.15–7.17 (m, 1 H), 7.27–7.34 (m, 2 H), 7.85–7.89 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 27.51, 27.79, 127.27, 127.39, 128.68, 129.52, 129.58, 130.34, 133.53, 137.56, 172.32.Compound 1h: 159 mg (63%); solid; mp 133–134 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.87–2.91 (m, 2 H), 2.96–3.00 (m, 2 H), 7.14–7.17 (m, 1 H), 7.22–7.25 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 28.99, 34.70, 124.43, 124.63, 127.29, 128.09, 128.59, 130.76, 133.01, 133.39, 172.51.
• 14 General Procedure for the Palladium-Catalyzed Carbonylative Cyclization of β-Bromo-α,β-unsaturated Carboxylic Acids Leading to Maleic AnhydridesTo a 50 mL stainless steel autoclave were added β-bromo-α,β-unsaturated carboxylic acid 1 (0.5 mmol), PdCl₂ (0.025 mmol), dppp (0.03 mmol), Et₃N (2 mmol), and AcOH (8 mL). After the system was flushed and then pressurized with CO to 10 atm, the reaction mixture was allowed to react at 120 °C for 3 h. The reaction mixture was poured into H₂O and extracted with EtOAc twice. The combined organic layer was dried over Na₂SO₄ and concentrated under reduced pressure. The crude mixture was purified by column chromatography (silica gel, hexane–EtOAc mixture) to afford maleic anhydrides 2. Except for 2f, all products are known.Compound 2f: 117 mg (99%); white solid; mp 87–88 °C. ¹H NMR (400 MHz, CDCl₃): δ = 1.27–1.34 (m, 4 H), 1.38–1.44 (m, 8 H), 1.75–1.81 (m, 4 H), 2.50 (t, J = 7.1 Hz, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 22.09, 22.23, 24.34, 25.14, 25.48, 145.10, 166.05. Anal. Calcd (%) for C₁₄H₂₀O₃: C, 71.16; H, 8.53. Found: C, 71.11; H, 8.67.