{
  "abstract": "Arylboronates are valuable synthetic intermediates for constructing C–C and C–X bonds. While the coppercatalyzed borylation of aryl halides has been reported, synthesizing 2-borylstyrenes from the corresponding aryl halides remains a challenge because the alkene is incompatible with conventional borylation methods. Herein, we turn this side reaction into the trigger of a productive cascade, enabling the copper-catalyzed borylation of 2-bromostyrenes with diboron reagents. The sequence comprises borylcupration, 1,3-bromine migration to form an arylcopper, intramolecular attack of the arylcopper on boron to give a cyclic borate, and copper-assisted debromination that restores the alkenyl group. Overall, the boryl group undergoes a 1,4-migration from C(sp3) to C(sp2), with the alkene serving as a transient relay. The detailed reaction mechanism for 1,4-boryl group migration was revealed by using density functional theory (DFT) calculations. The reaction tolerates chloro substituent and borylates dibromostyrenes site-selectively and is readily scalable to the gram scale.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering",
    "Kyoto University",
    "Graduate School of Engineering"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Go Yamagiwa"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Kazuhiko Semba"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Tetsuaki Fujihara",
      "orcid": "0000-0002-6687-2528"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/537w2e330sq30.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010958/v1",
  "fulltext_url": null,
  "id": "537w2e330sq30",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010958/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 Cross-Coupling Reactions"
    ]
  ],
  "openalex": "W7223326175",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010958/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/537w2e330sq30.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15010958",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010958/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic Cross-Coupling Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Copper-Catalyzed Borylation of 2-Bromostyrenes via 1,3-Bromine and 1,4-Boryl Group Migrations",
  "title_text": "Copper-Catalyzed Borylation of 2-Bromostyrenes via 1,3-Bromine and 1,4-Boryl Group Migrations",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/537w2e330sq30",
  "venue": "ChemRxiv",
  "versions": []
}