N-arylation reaction has become one of the key strategies in organic synthesis to access several molecules of biological, agrochemical, and medicinal importance. The century-old Ullmann reaction, for the synthesis of C–N has been realized as one of the foremost transition metal catalyzed coupling reaction. However, the limitation associated with the methodology has led to the evolution of several other synthetic strategies for the construction of C–N bonds. However, with the maturity of the copper chemistry, and the realization to look beyond palladium catalysis has led to the revival of the interest in the so-called Ullmann reaction. The need for a cheaper and sustainable catalytic system which makes use of the earth-abundant copper to catalyze the reaction has invigorated from its dormancy. Several research groups for past few years are incessantly working to develop more efficient and sustainable methodologies to address the pertinent issues of poor functional group tolerance, harsh reaction conditions prolonged reaction times associated with the Ullmann reaction and developed several sustainable strategies for the same. Therefore, this review focuses on the summary of the evolution of the Ullmann coupling reaction using earth abundant copper catalyst for the construction of C–N bond under sustainable conditions and provides an outline of the reaction strategies and mechanisms. Despite all these breakthroughs, there is still a demand for more efficient catalytic systems, more benign reaction conditions, as well as overcoming the challenges associated with the sterically and electronically demanding and substrates. This review will therefore inspire the future researchers to establish sustainable methodologies which can have applications on a large industrial scale.

N-芳基化反应已成为有机合成中获得几种具有生物、农业化学和医药重要性的分子的关键策略之一。具有百年历史的用于合成 C-N 的 Ullmann 反应已成为最重要的过渡金属催化偶联反应之一。然而，与该方法相关的局限性导致了其他几种用于构建 C-N 键的合成策略的发展。然而，随着铜化学的成熟，以及超越钯催化的认识，导致对所谓的乌尔曼反应的兴趣重新燃起。对利用地球上丰富的铜来催化反应的更便宜且可持续的催化系统的需求已从其休眠状态中恢复活力。过去几年，几个研究小组不断致力于开发更有效和可持续的方法，以解决功能基团耐受性差、恶劣的反应条件延长与 Ullmann 反应相关的反应时间等相关问题，并为此开发了几种可持续的策略。因此，本综述重点总结了在可持续条件下使用富含地球的铜催化剂构建 C-N 键的 Ullmann 偶联反应的演变，并概述了反应策略和机制。尽管取得了所有这些突破，但仍然需要更有效的催化系统、更温和的反应条件，以及克服与空间和电子要求和底物相关的挑战。