Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst

Abstract

A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.

Key words

nickel catalysis - cyanation - aromatic esters - aminoacetonitriles - coupling reaction

Publication History

Received: 24 August 2020

Accepted after revision: 17 September 2020

Article published online:
16 October 2020

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• 19 2-Naphthonitrile (3A); Typical Procedure A 20-mL glass vessel, equipped with a J. Young O-ring tap and a magnetic stirring bar, was charged with Ni(OAc)₂·4 H₂O (10.0 mg, 0.040 mmol, 10 mol%) and Na₂CO₃ (63.6 mg, 0.60 mmol, 1.5 equiv). The vessel was evacuated and its contents were dried with a heat gun. The vessel was then cooled to r.t., and filled with N₂ gas. Phenyl 2-naphthoate (1A; 99.3 mg, 0.40 mmol, 1.0 equiv), 2-morpholinoacetonitrile (2a: 100.9 mg, 0.80 mmol, 2.0 equiv), and dcypt (38.1 mg, 0.080 mmol, 20 mol%) were added, and the vessel was evacuated and refilled with N₂ gas three times. Toluene (1.6 mL) was added, and the vessel was sealed with the O-ring tap and heated at 160 °C in a nine-well reaction block for 24 h with stirring. The mixture was then cooled to r.t. and passed through a short silica-gel pad with EtOAc as an eluent. The filtrate was concentrated in vacuo, and the residue was purified by preparative TLC (hexane–EtOAc, 4:1) to give a white solid; yield: 46.3 mg (76%) (caution! The reaction should be conducted in a well-functioning fume hood to avoid exposure to the CO gas generated by the reaction. After the reaction, the vessel should be opened in the fume hood for the same reason.) ¹H NMR (400 MHz, CDCl₃): δ = 8.23 (s, 1 H), 7.93–7.87 (m, 3 H), 7.67–7.58 (m, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 134.6, 134.1, 132.2, 129.1, 129.0, 128.4, 128.0, 127.6, 126.3, 119.2, 109.3. HRMS (DART): m/z [M + NH₄]⁺ calcd for C₁₁H₁₁N₂: 171.0917; found: 171.0915.