“Recent Advances in TBHP‐Promoted C─N Bond Formation: A Review”

Abstract The formation of carbon–nitrogen (C─N) bonds in natural products and pharmaceuticals has become a key area of focus in organic chemistry. Among the various reagents explored, tert ‐butyl hydroperoxide (TBHP) has gained recognition as an efficient and cost‐effective oxidant. TBHP offers numerous benefits, including stability, environmental safety, and economic viability. TBHP serves as a versatile oxidising agent in numerous C─N bond forming reactions, including oxidative amination, and amidation. Its effectiveness spans a broad substrate scope, enabling the synthesis of diverse amines, amides, and other nitrogen‐ containing scaffolds. These compounds are essential building blocks in the development of anti‐biotics, anti‐cancer agents, anti‐virals, and anti‐bacterials. Over the past few decades, researchers have developed numerous catalytic systems and reaction conditions that leverage TBHP's oxidising power. These include metal‐catalyzed, metal‐free, photocatalytic approaches. Methodologies that utilize TBHP have successfully synthesized a wide range of essential amines and amides, demonstrating impressive chemoselectivity. This review comprehensively summarizes the advancements in C─N bond formation using TBHP as an oxidant over the past few decades. The significant progress in this field highlights TBHP's potential as a crucial reagent for synthesizing complex organic molecules, underscoring its utility in developing pharmaceuticals and natural products.