Synlett 2017; 28(20): 2759-2764
DOI: 10.1055/s-0036-1589007
letter
© Georg Thieme Verlag Stuttgart · New York

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

Suhelen Vásquez-Céspedesa, Michael Holtkampb, Uwe Karstb, Frank Glorius*a
  • aWestfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster, Germany   Email: glorius@uni-muenster.de
  • bWestfälische Wilhelms-Universität Münster, Instituts für Anorganische und Analytische Chemie, Corrensstraße 30, 48149 Münster, Germany
Further Information

Publication History

Received: 27 February 2017

Accepted after revision: 27 March 2017

Publication Date:
02 May 2017 (eFirst)

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

Supporting Information

 
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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.