Copper-Catalyzed C–H Stereoselective Cyanation of Alkenes by Using an α-Iminonitrile as a Cyanating Reagent

Abstract

The first copper-catalyzed cyanation through alkene C–H bond activation by using an α-iminonitrile as a cyanating agent has been realized. The approach efficiently constructs acrylonitriles in good yields with the advantages of high regioselectivity, cost-benefit, and operational simplicity.

Key words

copper catalysis - C–H activation - cyanation - iminonitriles - alkenes - acrylonitriles

• References and Notes

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• 19 3-Phenyl-3-pyridin-2-ylacrylonitrile; Typical ProcedureA solution of 1a (0.50 mmol), α-iminonitrile 2a (139.5 mg, 0.75 mmol), and Cu(TFA)₂ (1.0 mmol) in THF (2.0 mL) was stirred at 120 °C for 24 h, then cooled to r.t. The solvent was then evaporated in vacuo, and the residue was purified by column chromatography [silica gel, PE–EtOAc (9:1)] to give a brown oil; yield: 75 mg (73%).¹H NMR (400 MHz, CDCl₃): δ = 8.7 (d, J = 3.6 Hz, 1 H), 7.8 (t, J = 7.3 Hz, 1 H), 7.5 (d, J = 7.8 Hz, 1 H), 7.4–7.3 (m, 4 H), 7.3 (d, J = 7.2 Hz, 2 H), 5.8 (s, 1 H). ¹³C NMR (151 MHz, CDCl₃): δ = 161.2 (s), 155.1 (s), 150.0 (s), 137.7 (s), 136.8 (s), 130.5 (s), 128.8 (s), 128.4 (s), 125.0 (s), 124.4 (s), 117.4 (s), 97.3.