Silver-Catalyzed Synthesis of Nitriles from Carboxylic Acids and Cyanamides

Abstract

A concise and practical silver-catalyzed nitrogen-atom-transfer protocol was developed to access versatile nitriles from ubiquitous carboxylic acids with N-cyano-N-phenyl-p-toluenesulfonamide. This protocol complements the established carboxylic acids-to-nitriles conversion methods, which suffer from laborious steps, high temperatures (≥200 °C), or limited substrate scopes. This approach operates broadly across diverse aryl, alkenyl, and primary-, secondary-, or tertiary-alkyl carboxylic acids.

Key words

carboxylic acids - nitriles - silver - cyanamide - decarboxylation

Publication History

Received: 10 February 2023

Accepted after revision: 13 March 2023

Accepted Manuscript online:
13 March 2023

Article published online:
12 April 2023

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• 23 4-Methoxybenzonitrile (3a): Typical ProcedureIn an argon-filled glovebox, an oven-dried 4 mL vial equipped with a magnetic stirrer bar was charged with AgSbF₆ (3.4 mg, 5.0 mol%), 4-methoxybenzoic acid (1a, 0.2 mmol, 1.0 equiv), and NCTS (2, 65 mg, 0.24 mmol, 1.2 equiv). Toluene (600 μL) and dodecane (10 μL; internal standard) were added, and the vial was sealed and transferred out of the glove box. The mixture was stirred at 120 ℃ for 48 h, then cooled to r.t. The crude product was purified by column chromatography [silica gel, PE–EtOAc (10:1)] to give a white solid; yield: 79%.¹H NMR (400 MHz, CDCl₃): δ = 7.60–7.56 (m, 2 H), 6.97–6.92 (m, 2 H), 3.85 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 162.9, 134.1, 119.3, 114.8, 104.1, 55.6. HRMS-ESI: m/z [M + H]⁺ calcd for C₈H₈NO: 134.0600; found: 134.0596