Palladium-Catalyzed Oxidative Heck Coupling of Vinyl Pyridines with Aryl Boronic Acids

Abstract

An efficient methodology has been developed for the oxidative cross-coupling of vinyl pyridine with various boronic acids catalyzed by palladium. In this reaction, vinyl pyridines reacted with various aryl boronic acids in the presence of 10 mol% palladium(II) trifluoroacetate, 10 mol% 1,10- phenanthroline, and 1 equivalent silver(I) oxide, to give the corresponding aryl vinyl pyridine products as a single stereoisomer, with N,N-dimethylformamide as the solvent and under 1 atmosphere of oxygen gas. The aryl vinyl pyridine products were obtained in moderate to good yields after 24 hours. A mechanism for the reaction is proposed.

Key words

oxidative Heck coupling - palladium catalyst - vinyl pyridine - boronic acid

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• 16 Preparation of 3; General Procedure: Pd(TFA)₂ (0.02 mmol, 10 mol%), 1,10-phenanthroline (0.02 mmol, 10 mol%), Ag₂O (0.2 mmol, 1 equiv), phenyl boronic acid (0.3 mmol, 1.5 equiv), and 2-vinyl pyridine (0.2 mmol, 1 equiv) were added to a 10 mL round-bottom flask containing DMF (1 mL). The mixture was stirred for 24 h at 80 °C under 1 atmosphere of O₂. After cooling to r.t., the mixture was diluted with EtOAc (5 mL) and filtered through a plug of Celite. The filtrate was washed with sat. NH₄Cl (2 × 5 mL), and brine (5 mL). The organic layer was dried with anhydrous MgSO₄ and filtered. The crude product was obtained by evaporating the organic solvent under reduced pressure. The desired product was isolated by column chromatography (Et₂O–hexane, 3:7). Data for 3d: ¹H NMR (400 MHz, CDCl₃, 295 K): δ = 8.51 (d, J = 4.0 Hz, 1 H), 7.55 (td, J = 8.0, 1.6 Hz, 1 H), 7.53 (d, J = 16.4 Hz, 1 H, CH=CH), 7.44 (d, J = 8.4 Hz, 2 H), 7.32 (d, J = 8.4 Hz, 2 H), 7.31 (td, J = 8.4, 2.4 Hz, 1 H), 7.06 (d, J = 16 Hz, 1 H, CH=CH), 7.04 (td, J = 6.8 Hz, 1 H), 1.25 (s, 9 H). ¹³C{¹H} NMR (100 MHz, CDCl₃, 295 K): δ = 155.86, 151.58, 149.62, 136.49, 133.88, 132.57, 127.20, 126.88, 125.68, 121.91, 121.86, 34.71, 31.28.