Microwave-Assisted Hydrogen-Free Reductive Deiodination of Iodoarenes with Silicon-Nanoarray Palladium-Nanoparticle Catalyst

Abstract

The hydrogenolysis of iodoarenes using a silicon nanoarray palladium catalyst under microwave irradiation was investigated. When triethanolamine was used as the sacrificial reductant, the reaction proceeded via reductive deiodination under an aerobic atmosphere even without the presence of the explosive hydrogen gas, affording the corresponding hydrogen-substituted arenes in high yields. No reaction occurred in the absence of microwaves, indicating a noticeable microwave effect.

Key words

microwave - dehalogenation - deiodination - reductive dehalogenation - iodoarenes - triethanolamine - palladium - silicon nanowire array

• References and Notes

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• 20 General ProcedureSiNA-Pd (600 mol ppm) was added to a mixture containing 1 (0.85 mmol), TEOA (1.71 mmol), and dry DMF (3.0 mL) in a glass vial equipped with silicone rubber and polytetrafluoroethylene lids. The resulting reaction vial was irradiated with microwave at 130 °C for 1.5 h under an aerobic atmosphere. After the reaction, an aliquot was analyzed via GC in the presence of decane (for 1e) or mesitylene (for the other substrates) as the internal standards. Biphenyl (2f)Compound 2f was isolated using the following general procedure in the reaction of 1h (238 mg, 0.850 mmol). After the reaction was completed, the reaction mixture was cooled to 25 °C. Toluene (30 mL) was then added, and the resulting mixture was washed with 1 M HCl (5 × 10 mL). The organic layer was dried over MgSO₄ and evaporated in vacuo to obtain biphenyl (127 mg, 0.825 mmol, 97%). ¹H NMR (500 MHz, CDCl₃): δ = 7.60 (d, 4 H, J = 7.0 Hz, o-Ph), 7.44 (t, 4 H, J = 7.7 Hz, m-Ph), 7.35 (t, 2 H, J = 7.3 Hz, p-Ph). Using the same procedure with 1k (206 mg, 0.849 mmol), indole (2k, 72.1 mg, 0.615 mmol, 73%) was also obtained. ¹H NMR (500 MHz, CDCl₃): δ = 7.65 (d, 1 H, J = 8.0 Hz), 7.41 (d, 1 H, J = 8.0 Hz), 7.22–7.18 (m, 2 H), 7.12 (t, 1 H, J = 7.5 Hz), 6.56 (s, 1 H).