Reusable and Magnetic Palladium and Copper Oxide Catalysts in Direct ortho and meta Arylation of Anilide Derivatives

Dedicated to Prof. Victor Snieckus on the occasion of his 80^th birthday

Abstract

We report a general, direct C–H arylation of anilide derivatives using reusable palladium or copper oxide on magnetite as heterogeneous precatalysts. Highly selective ortho and meta arylations are achieved using electronically and sterically diverse diaryliodonium salts. Catalytically active soluble species from the heterogeneous precursors were detected by experimental techniques. Preliminary mechanistic investigation suggests different reaction pathways for each of the catalysts.

Key words

regioselective direct C–H arylation - reusable palladium catalyst - reusable copper oxide catalyst - leaching–redeposition - anilide derivatives

• References and Notes

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• 26 General Procedure for meta Arylation To a 10 mL Schlenk tube with a magnetic stirring bar was added N-(o-tolyl)pivalamide (57.3 mg, 0.30 mmol), diphenyliodonium triflate (258 mg, 0.60 mmol), and CuO/Fe₃O₄ (75 mg, 0.0083 mmol). Then, DCE (3.0 mL) was added under air and the reaction stirred at 70 °C for 22 h. The reaction mixture was allowed to cool to r.t., the catalyst was separated using a magnet, and the crude reaction was concentrated in vacuo and purified by flash column chromatography. Analytical Data for 3a ¹H NMR (300 MHz, CDCl₃): δ = 8.21 (d, J = 1.8, 1 H), 7.65–7.57 (m, 2 H), 7.45–7.36 (m, 2 H), 7.35–7.21 (m, 4 H), 2.30 (s, 3 H), 1.37 (s, 9 H). ¹³C NMR (75 MHz, CDCl₃): δ = 176.67, 140.79, 140.12, 136.36, 130.86, 128.77, 127.50, 127.31, 127.24, 123.49, 121.44, 39.98, 27.89, 17.47.
• 27 General Procedure for ortho Arylation To a 10 mL Schlenk tube with a magnetic stirring bar was added N-(o-tolyl)pivalamide (57.3 mg, 0.30 mmol), diphenyliodonium triflate (193.5 mg, 0.45 mmol), and Pd/Fe₃O₄ (90 mg, 0.014 mmol). Then, DCE (3.0 mL) was added under air and the reaction stirred at 70 °C for 22 h. The reaction mixture was allowed to cool to r.t., the catalyst separated using a magnet, and the crude reaction was concentrated in vacuo and purified by flash column chromatography. Analytical Data for 4a ¹H NMR (400 MHz, CDCl₃): δ = 7.46–7.36 (m, 3 H), 7.35–7.31 (m, 2 H), 7.31–7.27 (m, 2 H), 7.23–7.17 (m, 1 H), 6.84 (s, 1 H), 2.31 (s, 3 H), 1.15 (s, 9 H). ¹³C NMR (101 MHz, CDCl₃): δ = 176.82, 139.73, 139.65, 136.72, 132.94, 130.20, 129.11, 128.37, 127.74, 127.49, 127.12, 39.22, 27.63, 18.64.