{
  "abstract": "Chemo- and enantioselective mono-debrominative functionalization of 2,2-disubstituted 1,1-dibromoalkenes to access tetrasubstituted vinyl bromides remains a formidable challenge, owing to competitive double functionalization and the difficulty in achieving enantiocontrol when the gem-dibromoalkenyl moiety embodies a prochiral plane. Herein, we report a palladium-catalyzed asymmetric monocarbonylation of conformationally rigid, prochiral benzo[7]annulene-based gem-dibromoalkenes, furnishing inherently chiral tetrasubstituted benzo[7]annulene derivatives with excellent yields (up to 97%) and high enantioselectivities (up to 98:2 er). Notably, the inclusion of simple acid additives enables a switchable pathway divergence to double debrominative carbonylation, delivering inherently chiral trisubstituted vinyl carboxylic acids with equally good chemo- and enantiocontrol. This protocol is also applicable to unsymmetric gem-dibromoalkene substrates, affording the corresponding products with synthetically useful yields and enantioselectivities. Mechanistic studies, supported by DFT calculations, reveal that the acid-induced formation of a key alkylidene carbene-Pd-H species is pivotal for the pathway switch, followed by enantioselective carbene insertion into the Pd-H bond and subsequent CO insertion. This work not only provides a modular and divergent route to both tri- and tetrasubstituted inherently chiral benzo[7]annulene scaffolds, but also represents the first asymmetric desymmetrization of planarly prochiral gem-dibromoalkenes via palladium catalysis.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 5,
  "authors": [
    {
      "name": "Yu Luo"
    },
    {
      "name": "Xilong Wang"
    },
    {
      "name": "Yuanhang Zhang"
    },
    {
      "name": "Shuang Luo",
      "orcid": "0000-0003-0805-4479"
    },
    {
      "name": "Qiang Zhu",
      "orcid": "0000-0002-1243-2391"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/e5ysmzceya0q6.bib",
  "cited_by": 0,
  "doi": "10.1038/s41467-026-78226-0",
  "fulltext_url": "https://europepmc.org/articles/PMC13724673",
  "id": "e5ysmzceya0q6",
  "issns": [
    "2041-1723"
  ],
  "landing_url": "https://www.nature.com/articles/s41467-026-78226-0",
  "language": "eng",
  "licence": "CC-BY-NC-ND-4.0",
  "licence_label": "CC BY-NC-ND 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Article"
    ],
    [
      "openalex",
      "1605|Catalytic Cross-Coupling Reactions"
    ]
  ],
  "openalex": "W7218949491",
  "pdf_url": "https://www.nature.com/articles/s41467-026-78226-0_reference.pdf",
  "pmcid": "PMC13724673",
  "pmid": "42967917",
  "published": "2026-10-03",
  "publisher": "Springer Science and Business Media LLC",
  "ris": "https://research.draconitic.com/paper/e5ysmzceya0q6.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:38Z",
      "native_id": "10.1038/s41467-026-78226-0",
      "source": "crossref",
      "url": "https://www.nature.com/articles/s41467-026-78226-0"
    },
    {
      "first_seen": "2026-11-03T15:20:53Z",
      "native_id": "MED:42967917",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42967917"
    },
    {
      "first_seen": "2026-11-04T12:23:13Z",
      "native_id": "PMC13724673",
      "source": "pmc",
      "url": "https://doi.org/10.1038/s41467-026-78226-0"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic Cross-Coupling Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Enantioselective palladium-catalyzed carbonylation of gem-dibromoalkenes to chiral benzo[7]annulenes",
  "title_text": "Enantioselective palladium-catalyzed carbonylation of gem-dibromoalkenes to chiral benzo[7]annulenes",
  "type": "peer-reviewed",
  "updated_at": "2026-11-06T12:21:05Z",
  "url": "https://research.draconitic.com/paper/e5ysmzceya0q6",
  "venue": "Nature Communications",
  "versions": []
}