{
  "abstract": "C−H halogenation plays a central role in drug discovery. It enables rapid molecular diversification and provides a direct means to tune the metabolic and biological properties of drug candidates. However, selective halogenation of less reactive arenes remains challenging, particularly when aromatic and benzylic C−H bonds coexist in the same molecule. Here, we introduce a thioiminium salt-based Lewisbase catalyst that activates readily available N-halosuccinimides for selective aromatic and benzylic halogenation with complementary control. Notably, the method enables late-stage aromatic bromination of natural products, pharmaceuticals, peptides and heterocycles and can be extended to aromatic chlorination using N-chlorosuccinimide. The practicality of this method is demonstrated by four gramscale syntheses, catalyst recycling and post-synthetic diversification. Mechanistic and computational studies reveal distinct electrophilic and radical pathways, with the catalyst counter anion acting as a molecular switch for chemoselectivity between aromatic and benzylic bromination.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "name": "Debasis Sahoo"
    },
    {
      "name": "Upasi Goswami"
    },
    {
      "name": "Haren Konwar"
    },
    {
      "name": "Arnab Mondal"
    },
    {
      "name": "Avijit Maiti"
    },
    {
      "name": "Tuhin Patra",
      "orcid": "0000-0002-4783-7794"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/6gg16ry1jfq25.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010130/v1",
  "fulltext_url": null,
  "id": "6gg16ry1jfq25",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010130/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Catalytic C–H Functionalization Methods"
    ]
  ],
  "openalex": "W7221079678",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010130/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-08",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/6gg16ry1jfq25.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15010130",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010130/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic C–H Functionalization Methods",
      "subfield": "organic"
    }
  ],
  "title": "Thioiminium Salt Catalyzed Chemoselective Late Stage Halogenation Using N-Halosuccinimides",
  "title_text": "Thioiminium Salt Catalyzed Chemoselective Late Stage Halogenation Using N-Halosuccinimides",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/6gg16ry1jfq25",
  "venue": "ChemRxiv",
  "versions": []
}