{
  "abstract": "Direct C(sp3)–H functionalization of methylpyridines is intrinsically challenging. Herein, we report a transition-metal-free, silylboronate-mediated heterobenzylation of methylpyridines with aryl fluorides. The combination of a silylboronate and KOtBu enables direct C(sp3)–H/C(sp2)–F coupling under mild conditions, providing efficient access to structurally diverse azaarylmethanes. The reaction accommodates π-extended aryl fluorides, polyfluoroarenes, and various 4-alkylpyridines, including substrates bearing multiple potentially reactive C–H or C–F bonds, with useful levels of chemo- and regioselectivity. The method is also applicable to the late-stage functionalization of structurally complex molecules. Alkyl fluorides are also compatible via the C(sp3)–H/C(sp3)–F coupling reaction. Mechanistic studies, including aryl-halide comparison, radical-trapping, investigation of pronucleophile, Hammett plot, competition experiments, and DFT calculation support an ionic pathway involving generation of a heterobenzylic nucleophile followed by nucleophilic substitution of the C–F bond. For electronically neutral and electron-rich aryl fluorides, the observed reactivity is consistent with a concerted SNAr pathway. This strategy provides a complementary approach to conventional transition-metal-catalyzed heterobenzylic arylation and expands the synthetic utility of organofluorine compounds as coupling partners for C–C bond formation.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Nanopharmaceutical Sciences",
    "Nagoya Institute of Technology",
    "Department of Engineering"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Seishu Ochiai"
    },
    {
      "affs": [
        2,
        1
      ],
      "name": "Zhengyu Zhao",
      "orcid": "0009-0005-0933-6461"
    },
    {
      "affs": [
        2,
        1
      ],
      "name": "Norio Shibata"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/6r4yey1ezy7fy.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010838/v1",
  "fulltext_url": null,
  "id": "6r4yey1ezy7fy",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010838/v1",
  "language": null,
  "licence": "CC-BY-NC",
  "licence_label": "CC BY-NC",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Catalytic C–H Functionalization Methods"
    ]
  ],
  "openalex": "W7223168248",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010838/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-22",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/6r4yey1ezy7fy.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15010838",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010838/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic C–H Functionalization Methods",
      "subfield": "organic"
    }
  ],
  "title": "Direct C(sp3)–H/C(sp2)–F Cross-Coupling of Methylpyridines with Aryl Fluorides",
  "title_text": "Direct C(sp3)–H/C(sp2)–F Cross-Coupling of Methylpyridines with Aryl Fluorides",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/6r4yey1ezy7fy",
  "venue": "ChemRxiv",
  "versions": []
}