{
  "abstract": "Pyridine-fused, C( sp 3 )-rich bridged frameworks are privileged scaffolds in natural products and pharmaceutical compounds, yet their synthesis remains a formidable challenge due to prevailing step-intensive routes. Energy transfer (EnT)-catalysed dearomative cycloadditions offer a milder approach to increase saturation in feedstock (hetero)arenes. Current methods exploiting the 1,4-biradical reactivity of bicyclic azaarenes mainly focus on [4+2] cycloadditions. However, achieving higher-order cycloadditions, such as [4+ n ] ( n > 2), to construct pyridine-fused/bridged motifs, remains challenging. Here we report a cascade reaction combining a higher-order dearomative [5+4] photocycloaddition of bicyclic azaarenes and vinyl cyclopropanes with a formal [3,3]-sigmatropic rearrangement and a subsequent [2+2] photocycloaddition. This triple EnT-catalysed cascade provides a mild, one-pot protocol for efficiently accessing complex pyridine-fused/bridged pentacyclic motifs with excellent selectivity. Notably, the EnT-mediated formal [3,3]-sigmatropic rearrangement unveils a mechanistic paradigm in photochemical cascades. Mechanistic experiments and density functional theory studies support involvement of three sequential EnT steps, rationalizing the origin of regioselectivity and diastereoselectivity.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 9,
  "authors": [
    {
      "name": "Preeti Chahar"
    },
    {
      "name": "Utpal Kundu"
    },
    {
      "name": "Subhabrata Dutta"
    },
    {
      "name": "Niklas Hölter"
    },
    {
      "name": "Florian Boser"
    },
    {
      "name": "Fabian Hugel"
    },
    {
      "name": "Luca Stadtmann"
    },
    {
      "name": "Constantin Daniliuc"
    },
    {
      "name": "Frank Glorius"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/exk3kxb292900.bib",
  "cited_by": 0,
  "doi": "10.1038/s41929-026-01566-z",
  "fulltext_url": null,
  "id": "exk3kxb292900",
  "issns": [
    "2520-1158"
  ],
  "landing_url": "https://hal.science/hal-05796256v1",
  "language": "en",
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "hal",
      "0.chim"
    ],
    [
      "openalex",
      "1605|Radical Photochemical Reactions"
    ]
  ],
  "openalex": "W7167835357",
  "pdf_url": "https://www.nature.com/articles/s41929-026-01566-z.pdf",
  "pmcid": null,
  "pmid": null,
  "published": "2026-07-09",
  "publisher": "Nature Publishing Group",
  "ris": "https://research.draconitic.com/paper/exk3kxb292900.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:55Z",
      "native_id": "hal-05796256",
      "source": "hal",
      "url": "https://hal.science/hal-05796256v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Radical Photochemical Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Triple energy transfer-enabled dearomative cycloaddition/rearrangement cascade of bicyclic azaarenes to structurally complex products",
  "title_text": "Triple energy transfer-enabled dearomative cycloaddition/rearrangement cascade of bicyclic azaarenes to structurally complex products",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:17:55Z",
  "url": "https://research.draconitic.com/paper/exk3kxb292900",
  "venue": "Nature Catalysis",
  "versions": []
}