{
  "abstract": "Organocatalytic methods operating via α,β-unsaturated acyl azolium intermediates are extensively studied in organic chemistry and typically proceed through E-configured intermediates that dictate the stereochemical outcome of the final product. To date, the use of this species within enzymatic systems is restricted to a single natural biosynthetic pathway. Herein, we report an example of a versatile new-to-nature biocatalytic transformation that harnesses an α,β-unsaturated acyl azolium intermediate within the active site of a thiaminedependent enzyme. Remarkably, this enzymatic environment favors the formation of the less accessible Z-acyl azolium, enabling the highly selective synthesis of Z-α,β-unsaturated acids via redox hydrolysis of α-bromoenals. The protocol features a broad substrate scope spanning aromatic and aliphatic substrates, all while maintaining excellent Z/E ratios.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, Freiestrasse 3, Bern, Switzerland, 3012"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Laura Kqiku",
      "orcid": "0000-0001-6422-9785"
    },
    {
      "affs": [
        0
      ],
      "name": "Joel Zobrist"
    },
    {
      "affs": [
        0
      ],
      "name": "Francesca Paradisi",
      "orcid": "0000-0003-1704-0642"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/7fq0byzvma7r5.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008234/v1",
  "fulltext_url": null,
  "id": "7fq0byzvma7r5",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008234/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",
      "1312|Enzyme Catalysis and Immobilization"
    ]
  ],
  "openalex": "W7207662352",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008234/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-03",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/7fq0byzvma7r5.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008234",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008234/v1"
    }
  ],
  "subjects": [
    {
      "field": "biochemistry",
      "origin": "openalex:1312|Enzyme Catalysis and Immobilization",
      "subfield": "molecular-biology"
    }
  ],
  "title": "New-to-Nature Transformation for the Z-Selective Synthesis of Unsaturated Acids via Acyl Azolium Intermediates",
  "title_text": "New-to-Nature Transformation for the Z-Selective Synthesis of Unsaturated Acids via Acyl Azolium Intermediates",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/7fq0byzvma7r5",
  "venue": "ChemRxiv",
  "versions": []
}