Microwave-Assisted Copper-Catalyzed Electrophilic Amination of Arylboronic Acids: A Rapid Approach to Arylhydrazides

Abstract

We present a copper-catalyzed rapid and efficient method for the electrophilic amination of arylboronic acids with azodicarboxylates under microwave irradiation to synthesize aryl-substituted hydrazines. This transformation encompasses a wide range of substituted boronic acids and azodicarboxylates to provide the corresponding products in good to excellent yields. The key features of this reaction are its broad substrate scope, high functional-group tolerance, good to excellent yields, and short reaction time.

Keywords

amination - boronic acids - copper catalysis - diethyl azodicarboxylate - microwave-assisted

Publication History

Received: 25 October 2024

Accepted after revision: 09 January 2025

Accepted Manuscript online:
09 January 2025

Article published online:
21 February 2025

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• 15 Arylhydrazides 3a–z; General Procedure An oven-dried, single-necked, round-bottomed flask containing a magnetic stirrer bar was charged with the appropriate arylboronic acid 1 (0.3 mmol), dialkyl azodicarboxylate 2 (0.2 mmol), Cu(OAc)₂∙H₂O (10 mol%), and MeCN (2 mL) under air. The flask was fitted with a condenser, and the mixture was vigorously stirred and subjected to microwave heating (400 W) at 80 °C for 20 min. When the reaction was complete, the mixture was filtered through a Celite pad with EtOAc as the washing solvent. The solvent was evaporated under reduced pressure, and the residue was purified by column chromatography [silica gel (100–200 mesh), PE–EtOAc]. Diethyl 1-Phenylhydrazine-1,2-dicarboxylate (3a) Yellow oil; yield: 99%. ¹H NMR (500 MHz, CDCl₃): δ = 7.60 (s, 1 H), 7.41 (d, J = 8.0 Hz, 2 H), 7.31 (t, J = 7.8 Hz, 2 H), 7.18 (t, J = 7.4 Hz, 1 H), 4.20 (dq, J = 14.6, 7.1 Hz, 4 H), 1.24 (t, J = 7.2 Hz, 6 H). ¹³C NMR (126 MHz, CDCl₃): δ = 156.59, 155.14, 141.81, 128.81, 126.54, 124.48, 63.18, 62.45, 14.59. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₇N₂O₄: 253.1183; found: 253.1185