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

Bhargav Desai; Akshay Bharodiya; Shruti Seshathre; Raj N. Patel; Bharatkumar Dholakiya; Piyushkumar Satani; Vinaykumar Kanchupalli; Togati Naveen

doi:10.1055/a-2513-8629

Synlett, Table of Contents

Synlett 2025; 36(09): 1252-1256
DOI: 10.1055/a-2513-8629

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

Bhargav Desai

^aDepartment of Chemistry, Sardar Vallabhbhai National Institute of Technology (SVNIT), Surat 395 007, Gujarat, India

,

Akshay Bharodiya

^aDepartment of Chemistry, Sardar Vallabhbhai National Institute of Technology (SVNIT), Surat 395 007, Gujarat, India

,

Shruti Seshathre

^bDepartment of Process Chemistry, National Institute of Pharmaceutical Education and Research (NIPER), Hyderabad 500 037, Telangana, India

,

Raj N. Patel

^cNatural Products and Green Chemistry Division, Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI), Bhavnagar 364 002, Gujarat, India

,

Bharatkumar Dholakiya

^aDepartment of Chemistry, Sardar Vallabhbhai National Institute of Technology (SVNIT), Surat 395 007, Gujarat, India

,

Piyushkumar Satani

^aDepartment of Chemistry, Sardar Vallabhbhai National Institute of Technology (SVNIT), Surat 395 007, Gujarat, India

,

Vinaykumar Kanchupalli

^bDepartment of Process Chemistry, National Institute of Pharmaceutical Education and Research (NIPER), Hyderabad 500 037, Telangana, India

,

Togati Naveen

^aDepartment of Chemistry, Sardar Vallabhbhai National Institute of Technology (SVNIT), Surat 395 007, Gujarat, India

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Abstract

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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

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References and Notes

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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

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