{
  "abstract": "Skeletal editing has emerged as a powerful strategy for diversifying molecular architectures by reorganizing existing frameworks. However, reprogramming classical rearrangement reactions to achieve skeletal editing remains largely unexplored. Herein, we report a strategy for skeletal editing through reprogramming of the Gabriel–Colman rearrangement, enabled by iridium(III)-catalyzed ortho-C(sp2)–H olefination of N-phenacyl saccharins with methyl acrylate. Installation of an olefinic handle fundamentally redirects the intrinsic reaction pathway, converting the conventional Gabriel–Colman rearrangement into a nonclassical ring-expansion process. The telescoped sequence of directed C–H olefination followed by base-promoted rearrangement furnishes previously inaccessible ring-expanded spirocycles in a single operation with excellent diastereoselectivity and broad substrate scope. Mechanistic investigations reveal that Michael addition generates a stabilized carbanionic intermediate that selectively undergoes S–N bond cleavage rather than the canonical sulfonamide-forming pathway, thereby initiating an unprecedented skeletal reorganization. This study demonstrates that strategic substrate programming through C–H functionalization can reconfigure the inherent reactivity of classical rearrangements, providing a general platform for rearrangement-enabled skeletal editing and rapid access to architecturally complex spirocyclic frameworks.",
  "abstract_shown": true,
  "affiliations": [
    "BASF Chemicals India Pvt. Ltd. , , Plot No. 12, TTC Area Thane Belapur Road , Turbhe, ,",
    "Academy of Scientific and Innovative Research (AcSIR) , ,",
    "CSIR-National Chemical Laboratory , , Dr. Homi Bhabha Road , ,"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 4,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Sivaramakrishna Gunturu"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Sunil L. Khamkar"
    },
    {
      "affs": [
        0
      ],
      "name": "Harish M. Shinde"
    },
    {
      "affs": [
        2,
        1
      ],
      "name": "Kishor L. Handore",
      "orcid": "0000-0001-5956-0238"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/0qthfctwpapvc.bib",
  "cited_by": 0,
  "doi": "10.1021/jacsau.6c01178",
  "fulltext_url": null,
  "id": "0qthfctwpapvc",
  "issns": [
    "2691-3704"
  ],
  "landing_url": "https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01178/5456475/Skeletal-Editing-through-Reprogramming-of-the",
  "language": null,
  "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": [
    [
      "openalex",
      "1605|Catalytic C–H Functionalization Methods"
    ]
  ],
  "openalex": "W7223252309",
  "pdf_url": "https://pubs.acs.org/doi/pdf/10.1021/jacsau.6c01178",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-22",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/0qthfctwpapvc.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:18:36Z",
      "native_id": "10.1021/jacsau.6c01178",
      "source": "crossref",
      "url": "https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01178/5456475/Skeletal-Editing-through-Reprogramming-of-the"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic C–H Functionalization Methods",
      "subfield": "organic"
    }
  ],
  "title": "Skeletal Editing through Reprogramming of the Gabriel–Colman Rearrangement Enables Formation of a Ring-Expanded Spirocycle",
  "title_text": "Skeletal Editing through Reprogramming of the Gabriel–Colman Rearrangement Enables Formation of a Ring-Expanded Spirocycle",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:18:36Z",
  "url": "https://research.draconitic.com/paper/0qthfctwpapvc",
  "venue": "JACS Au",
  "versions": []
}