Transition-metal-catalyzed direct transformation of inert C−H bond has revolutionized the arsenal of main-stream organic synthesis, providing a new upfront to forge structurally enriched and biologically relevant scaffolds in a step- and atom-economical way. Past decades have accounted for the major developments in this realm, proclaiming excellent site-selectivity by exploiting a variety of coordinating directing groups (DGs). Consideration of versatile, abundant, sp³-hybridized free-amine (−NH₂) functionality for the same purpose has always been a formidable task owing to its innate reactivity. In recent years, free-amine functionality has emerged as a potent DG for a wide range of C−C and C-heteroatom bonds formations and annulation cascades. In this review article, we have discussed the advancements of free-amine directed C−H activation/functionalization reactions towards biaryl frameworks made within a decade (2012 to 2021).

中文翻译：

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过渡金属催化的游离胺 (-NH2) 定向 C-H 键活化和联芳基骨架的功能化

过渡金属催化的惰性 C−H 键的直接转化彻底改变了主流有机合成的武器库，为以逐步和原子经济的方式锻造结构丰富且与生物相关的支架提供了新的前沿。在过去的几十年中，该领域取得了重大进展，通过利用各种协调指导组 (DG) 宣布了出色的站点选择性。考虑多功能、丰富的 sp ^{3 -}杂化游离胺 (-NH ₂) 由于其天生的反应性，用于相同目的的功能一直是一项艰巨的任务。近年来，游离胺官能团已成为广泛的 C-C 和 C-杂原子键形成和环化级联的有效 DG。在这篇评论文章中，我们讨论了在十年内（2012 年至 2021 年）针对联芳骨架的游离胺导向的 CH 活化/官能化反应的进展。