{
  "abstract": "The Ferrier rearrangement of 1,2-unsaturated monosaccharides (glycals) to 2,3-unsatured glycosides, is important for the synthesis of pharmaceuticals and natural products. Mechanistically, the nucleophilic substitution proceeds via a cationic intermediate, the “Ferrier cation”, whose structure is difficult to capture with conventional analytical techniques. Here, we characterize the Ferrier cations of glucal and galactal building blocks involving aliphatic acyl protecting groups (pivaloyl-, levulinoyl- and chloroacetyl esters) using cryogenic gas-phase infrared spectroscopy. Comparing experimental and computed spectra of candidate structures, we established that all intermediates are stabilized by interactions of the C4 acyl protecting group with the C3 carbon of the pyranose ring (neighboring participation), potentially steering the stereochemical outcome of the Ferrier rearrangement. The resulting C4-C3-dioxolenium ion structure appears to be general to aliphatic acyl protecting groups, contributing to our fundamental understanding of Ferrier rearrangement reactions.",
  "abstract_shown": true,
  "affiliations": [
    "Institute of Chemistry and Biochemistry, Freie Universität Berlin, Altensteinstraße 23a, Berlin, Germany, 14195",
    "Department of Molecular Physics, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, Berlin, Germany, 14195",
    "Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, Potsdam, Germany, 14476"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 9,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Niklas Geue",
      "orcid": "0000-0002-5216-8353"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Kim Greis"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Sabrina Omoregbee-Leichnitz"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Carla Kirschbaum"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Julinton Sianturi"
    },
    {
      "affs": [
        0
      ],
      "name": "Shenchuang Wang"
    },
    {
      "affs": [
        1
      ],
      "name": "Gert von Helden"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Peter H. Seeberger"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Kevin Pagel"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/bh64bw6fxfkr6.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009377/v1",
  "fulltext_url": null,
  "id": "bh64bw6fxfkr6",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009377/v1",
  "language": null,
  "licence": "CC-BY-NC",
  "licence_label": "CC BY-NC",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Carbohydrate Chemistry and Synthesis"
    ]
  ],
  "openalex": "W7214083738",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009377/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/bh64bw6fxfkr6.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009377",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009377/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Carbohydrate Chemistry and Synthesis",
      "subfield": "organic"
    }
  ],
  "title": "Ferrier Rearrangement Intermediates Featuring Aliphatic Acyl Protecting Groups",
  "title_text": "Ferrier Rearrangement Intermediates Featuring Aliphatic Acyl Protecting Groups",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/bh64bw6fxfkr6",
  "venue": "ChemRxiv",
  "versions": []
}