{
  "abstract": "The photochemistry of carbonyl compounds underpins a wide range of modern synthetic transformations. However, photoinduced rearrangements, despite their unique potential for skeletal reorganization, remain conspicuously underexplored. Here, we show that fluorine can be used as a design principle to divert these reactions from established photochemical pathways. Mechanistic investigations combining experimental, spectroscopic and computational approaches support an unusual singlet excited state pathway involving initial cyclization followed by skeletal rearrangement. This sequence enables the formation of carbonyl ylide 1,3-dipoles, while exhibiting a pronounced increase in polarization along the reaction path. The high efficiency and selectivity of the process provide an attractive platform for isomerization and photoclick chemistry, while its compatibility with water and oxygen broadens the potential for bioorthogonal applications.",
  "abstract_shown": true,
  "affiliations": [
    "Department Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, Mainz, Germany, 55128",
    "Instituto de Investigación Química de la Universidad de La Rioja (IQUR), Universidad de La Rioja Madre de Dios"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Abhilash Pedada"
    },
    {
      "affs": [
        0
      ],
      "name": "Jérémy Pecourneau"
    },
    {
      "affs": [
        1
      ],
      "name": "Alejandro García-Eguizábal"
    },
    {
      "affs": [
        0
      ],
      "name": "Daniil Tkatchev"
    },
    {
      "affs": [
        1
      ],
      "name": "Raúl Losantos"
    },
    {
      "affs": [
        0
      ],
      "name": "Christoph Kerzig"
    },
    {
      "affs": [
        1
      ],
      "name": "Ignacio Funes-Ardoiz"
    },
    {
      "affs": [
        0
      ],
      "name": "Johannes M. Wahl",
      "orcid": "0000-0001-8284-3965"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/fs0c2273fgvkd.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008235/v1",
  "fulltext_url": null,
  "id": "fs0c2273fgvkd",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008235/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",
      "1606|Chemical Reactions and Mechanisms"
    ]
  ],
  "openalex": "W7207826814",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008235/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-03",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/fs0c2273fgvkd.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008235",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008235/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1606|Chemical Reactions and Mechanisms",
      "subfield": "physical"
    }
  ],
  "title": "Fluorine-Enabled Photochemical Generation of Carbonyl Ylide 1,3-Dipoles",
  "title_text": "Fluorine-Enabled Photochemical Generation of Carbonyl Ylide 1,3-Dipoles",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/fs0c2273fgvkd",
  "venue": "ChemRxiv",
  "versions": []
}