Pd/C-Catalyzed Homocoupling Reaction for the Synthesis of Symmetrical Biaryl Diamides

Abstract

Pd/C was found to be an efficient and convenient metal catalyst in the homocoupling reaction for the synthesis of symmetrical biaryl diamides. The catalyst system Pd/C–KOAc showed high catalytic activity, and a variety of symmetrical biaryl diamides were conveniently synthesized from 2-halo-N-phenylbenzamides in moderate to good yields.

Key words

Pd/C - homocoupling reaction - symmetrical biaryl diamides - 2-halo-N-phenylbenzamides - recyclability

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• 20 General Procedure for the Synthesis of Symmetrical Biaryl Diamides An oven-dried Schlenk tube equipped with a Teflon valve was charged with a magnetic stir bar, 10% Pd/C (10% wt% of a), 2-halo-N-phenylbenzamides a (0.3 mmol) and KOAc (0.6 mmol). The tube was placed under vacuum for 20 min and backfilled with N₂. Then DMA (2.0 mL) was added through a syringe. The reaction mixture was stirred at 125 °C for 20 h. The reaction was monitored by TLC. When 2-halo-N-phenylbenzamides a consumed completely, the reaction was stopped and cooled to r.t., EtOAc (40 mL) was added, and the mixture was washed with brine (3 × 20 mL). The organic phase was dried over Na₂SO₄ and concentrated. The residue was purified directly by column chromatography on silica gel to give the pure products b (PE–EtOAc = 2:1, v/v). Typical Analytical Data of N ²,N ²′-Diphenyl-[1,1′-biphenyl]-2,2′-dicarboxamide (1b) ¹H NMR (400 MHz, CDCl₃): δ = 9.00 (s, 2 H), 7.69 (d, J = 7.2 Hz, 2 H), 7.45–7.58 (m, 8 H), 7.26 (t, J = 7.6 Hz, 4 H), 7.17 (d, J = 8.4 Hz, 2 H), 7.07 (t, J = 7.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 168.46, 139.21, 138.03, 136.20, 130.34, 129.86, 129.04, 128.27, 127.33, 124.61, 120.08.