Copper Iodide Mediated Cyanation of Arylboronic Acids and Aryl Iodides with Ethyl (Ethoxymethylene)cyanoacetate as Cyanating Agent

Abstract

An efficient copper iodide mediated cyanation of arylboronic acids and aryl iodides with ethyl (ethoxymethylene)cyanoacetate as cyanating agent has been developed. The reaction involves a C(sp²)–CN bond cleavage and tolerates a wide range of functional groups, affording the corresponding aryl nitriles in moderate to excellent yields.

Key words

copper - nitriles - transition metals - cleavage - arenes

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• 12 Typical Procedure for the Synthesis of Compound 3a To a 25 mL round-bottom flask was added the mixture of boronic acid 1a (0.3 mmol), ethyl 2-cyano-3-ethoxyacrylate (2a, 0.6 mmol), CuI (0.3 mmol), t-BuOOH (0.6 mmol) in DMF (2 mL) successively. The mixture was stirred at 130 °C for 24 h under air. After the reaction was completed, the mixture was cooled to room temperature, diluted with H₂O (15 mL), and then extracted with CH₂Cl₂ (3 × 5 mL). The organic extract was washed with H₂O (3 × 10 mL) and dried over anhydrous Na₂SO₄. After removal of the CH₂Cl₂ in vacuum, the crude product thus obtained was purified by column chromatography on silica gel using PE–EtOAc as eluent to give the desired product 3a as a white solid; yield 72%; mp: 86–87 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.73–7.66 (m, 4 H), 7.59 (d, J = 7.3 Hz, 2 H), 7.51–7.43 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 145.6, 139.0, 132.5, 129.0, 128.6, 127.6, 127.1, 118.8, 110.8. IR (KBr): 2227, 1605, 1484, 1400, 844, 769, 736, 699, 564, 518 cm^–1. MS (EI): m/z = 179 (100) [M⁺], 151, 126, 113, 89, 76, 63.