Cyanation and Hydrolysis Cascade of Aryl Bromides with Cuprous Cyanide to Access Primary Amides

Abstract

A convenient and efficient approach for the cyanation and hydrolysis of aryl bromides to afford primary amides was developed, in which cuprous cyanide is used as a cyanide source and a catalyst. It has the advantages of excellent functional-group compatibility, medium to high yields, a one-pot procedure, and a non-noble-metal catalyst. The reaction could be performed on a gram scale to give N-allyl-N-methyl-5-nitroisophthalamide in a 73% yield.

Key words

primary amides - aryl bromides - copper(I) cyanide - copper catalysis - one-pot reaction - late-stage modification

Publication History

Received: 07 April 2023

Accepted after revision: 10 May 2023

Article published online:
04 July 2023

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• 22 Aromatic Amides 2a–x; General Procedure A dry two-necked flask was charged with the appropriate bromide 1a–x (3.0 mmol, 1.0 equiv), Et₃N (485.6 mg, 4.8 mmol, 1.6 equiv), CuCN (483.6 mg, 5.4 mmol, 1.8 equiv), and H₂O (0.6 mL) under a positive pressure of N₂, and then subjected to three evacuation/backfilling cycles under high vacuum. Ultra-dry NMP (6.0 mL) was injected into the flask from a syringe, and the flask was placed in a preheated oil bath at 170 ℃ for 18–24 h while the progress of the reaction was monitored by TLC. The mixture was then cooled to r.t., diluted with sat. aq NaCl (15 mL) and EtOAc (15 mL), and filtered through a layer of Celite, eluting with EtOAc. The filtrate was extracted with EtOAc (3 × 30 mL), and the combined organic layers were washed with H₂O and sat. aq NaCl, then dried (Na₂SO₄), filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography [silica gel, EtOAc–hexane (1.2:1, v/v)]. Benzamide (2a) Colorless flake crystals; yield: 294.4 mg (81%). ¹H NMR (400 MHz, DMSO-d₆ ): δ = 7.97 (s, 1 H), 7.89–7.86 (m, 2 H), 7.54–7.51 (m, 1 H), 7.44 (dd, J = 8.0, 6.6 Hz, 2 H), 7.36 (s, 1 H). ¹³C{¹H} NMR (100 MHz, DMSO-d₆ ): δ = 167.9, 134.3, 131.2, 128.2, 127.5. HRMS (ESI-TOF): m/z [M + H]⁺ calcd for C₇H₈NO: 122.0600; found: 122.0603.