The pace and the scope of new molecules design is often constrained by limitations in synthetic chemistry. The azaheterocyclic amidrazones are of particular interest for bioisosteric considerations in drug discovery. However, the lack of efficient synthetic access has undoubtedly hampered their occurrence in the drug chemical space. Our current results describe a robust synthetic access relying on cyclization of aminohydrazine in presence of various orthoesters by either metal free‐ or metal‐catalyzed condensations. This optimized synthetic access to cyclic amidrazones as original scaffold should inspire the chemist community and further drive innovation in the design of molecular structure for many applications (for example, drugs, materials, dyes).
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