Recent Advances in Copper-Catalysed Hydrolysis of Aryl Halides to Phenols

Abstract

Phenol and its derivatives are indispensable bulk and fine-chemical intermediates, widely used in the synthesis of pharmaceuticals, agrochemicals, polymeric materials, dyes, and a broad range of specialty chemicals [1, 2]. Conventional manufacturing routes to phenols generally suffer from multistep operations, harsh conditions, high energy consumption, substantial environmental burdens, and safety concerns [3, 4]. In recent years, the direct hydrolysis of aryl halides to phenols under transition-metal catalysis has attracted considerable attention owing to its step and atom economy as well as its potential environmental benefits [5, 6]. Among various metals, copper has emerged as a focal point because of its low cost, relatively low toxicity, diverse accessible oxidation states, and flexible catalytic pathways [7, 8]. With the rational design of novel ligands and additives, the growing use of greener media, and breakthroughs in nanocatalysis and single-atom catalysis, copper-catalysed hydrolysis has been realised under increasingly mild conditions, with continuously expanding substrate scope, enhanced functional-group tolerance, and improved catalytic efficiency and selectivity [9, 10]. This review provides a systematic summary of research progress in copper-catalysed hydrolysis of aryl halides to phenols, with emphasis on mechanistic understanding, the key components of catalytic systems, and optimisation of reaction conditions, followed by a perspective on current challenges and future directions.