1,2,3‐Benzotriazoles could undergo ring cleavage to form ortho‐amino arenediazonium or α‐diazo‐imine species via a Dimroth‐type equilibrium. Historically, the synthetic potential of this unique reactivity had remained underdeveloped. Recently, some new strategies have been developed to effect the ring‐opening chemistry of benzotriazoles in more practical manners. A wide range of conceptually novel and synthetically useful reactions have been developed, which enable the access to diverse valuable heterocycles and ortho‐amino arene derivatives. As one of the players in this field, our group has also contributed a series of intriguing transition‐metal‐catalyzed denitrogenative functionalizations of benzotriazoles. In this account, we aim to provide an overview of the ring‐opening chemistry of benzotriazoles, with a focus on relevant works published in the past decade. In order to show a whole picture of the research field, some pioneering works in its developing history will also be discussed briefly.

中文翻译：

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苯并三唑的开环化学的复兴：旧瓶装新酒

1,2,3-苯并三唑可通过Dimroth型平衡进行开环裂解形成邻氨基苯二氮杂或α-重氮亚胺类。从历史上看，这种独特反应性的合成潜能一直未被开发。最近，已开发出一些新策略以更实际的方式影响苯并三唑的开环化学。已经开发了范围广泛的概念上新颖的和合成上有用的反应，其使得能够获得各种有价值的杂环和邻位-氨基芳烃衍生物。作为该领域的参与者之一，我们小组还为苯并三唑的一系列有趣的过渡金属催化的脱氮官能化做出了贡献。因此，我们旨在概述苯并三唑的开环化学，并重点介绍过去十年中发表的相关著作。为了展示整个研究领域的概况，还将简要讨论其发展历史中的一些开拓性著作。