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Here, we report a general and efficient strategy for the first\u2010time conversion of nitroarenes into pharmaceutically relevant pyridine heterocycles via a nitrene\u2010mediated transformation. This process is driven by a bio\u2010inspired iron\u2013porphyrin catalyst that uniquely serves as a singlet oxygen reservoir, enabling the formation of aminopyridines via C5\u2010carbon deletion through a controlled ring\u2010editing cascade. The unprecedented selective C5\u2010carbon deletion provides a powerful new retrosynthetic logic for heterocycle construction. The reaction proceeds under mild conditions, tolerates a wide range of functional groups, and offers broad substrate scope with high regioselectivity. Furthermore, the method's ability to efficiently convert nitroarenes into bioactive pyridine scaffolds via ipso\u2010carbon deletion underscores its practicality and step economy. This modular platform also streamlines the synthesis of drug\u2010like scaffolds from simple building blocks, as demonstrated by the late\u2010stage functionalization of nimesulide derivatives with improved molecular docking and binding profiles. Overall, this work showcases a distinctive catalytic paradigm for heterocycle construction with direct implications for pharmaceutical development and molecular remodeling.<\/jats:p>","DOI":"10.1002\/anie.202517867","type":"journal-article","created":{"date-parts":[[2025,12,24]],"date-time":"2025-12-24T15:03:09Z","timestamp":1766588589000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["A General Strategy to Access Pharmaceutically Relevant Pyridines from Nitroarenes"],"prefix":"10.1002","volume":"65","author":[{"given":"Argha","family":"Saha","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Bombay  Powai, Mumbai 400076 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Avishek","family":"Pan","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Bombay  Powai, Mumbai 400076 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Devika","family":"Ghosh","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Bombay  Powai, Mumbai 400076 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anirban","family":"Pal","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Bombay  Powai, Mumbai 400076 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Srimanta","family":"Guin","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Bombay  Powai, Mumbai 400076 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Archana Kumari","family":"Redhu","sequence":"additional","affiliation":[{"name":"Clinical Pharmacology Laboratory Advanced center for Treatment Research and Education in Cancer (ACTREC). 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