{
  "abstract": "Selectivity between competing thermal reactions is, by textbook account, set either by the relative free energies of the products (thermodynamic control) or by those of the transition states leading to them (kinetic control). Neither principle applies to endergonic reactions: a non-equilibrium product concentration is maintained at the expense of an energy source, with species forming and decomposing simultaneously. Here we show that a third, distinct principle governs selectivity in endergonic reactions: the degree of turnover-frequency control, exerted by each intermediate of the kinetic barrier diagram associated to the reaction network. We demonstrate this principle experimentally, using a dynamic combinatorial system in which two furan derivatives compete for maleic acid in an endergonic Diels–Alder reaction driven by carbodiimide hydration. The product distribution depends on whether the system is at equilibrium or driven, and can be inverted under fueling. Kinetic measurements and analytical modeling quantitatively capture the observed selectivities – including counterintuitive non-monotonic responses – and recover thermodynamic and kinetic control as limiting cases.",
  "abstract_shown": true,
  "affiliations": [
    "Institut de Science et d’Ingénierie Supramoléculaires (ISIS), University of Strasbourg, CNRS & iCFRC, UMR, 8 allée Gaspard, Strasbourg, France, 67000",
    "State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry",
    "Jilin University",
    "Department of Chemical Engineering, Delft University of Technology, Mekelweg 5, Delft, Netherlands, 2628",
    "Dipartimento di Chimica Industriale “Toso Montanari, Università di Bologna, via P. Gobetti 85, Bologna, Italy, I-40129",
    "Dipartimento di Chimica “G. Ciamician, Università di Bologna, via P. Gobetti 85, Bologna, Italy, I-40129"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Zhipeng Li"
    },
    {
      "affs": [
        0,
        3
      ],
      "name": "Shuntaro Amano"
    },
    {
      "affs": [
        0
      ],
      "name": "Shaymaa Al Shehimy"
    },
    {
      "affs": [
        0
      ],
      "name": "Malak Rafieq Jaber"
    },
    {
      "affs": [
        4
      ],
      "name": "Leonardo Andreoni"
    },
    {
      "affs": [
        5
      ],
      "name": "Serena Silvi"
    },
    {
      "affs": [
        1,
        2
      ],
      "name": "Zhong-Yuan Lu"
    },
    {
      "affs": [
        0
      ],
      "name": "Giulio Ragazzon"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/3x776zecpt6sg.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010447/v1",
  "fulltext_url": null,
  "id": "3x776zecpt6sg",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010447/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Supramolecular Chemistry and Complexes"
    ]
  ],
  "openalex": "W7221748062",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010447/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-14",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/3x776zecpt6sg.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15010447",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010447/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Supramolecular Chemistry and Complexes",
      "subfield": "organic"
    }
  ],
  "title": "An experimentally-validated principle for selectivity in endergonic reactions",
  "title_text": "An experimentally-validated principle for selectivity in endergonic reactions",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/3x776zecpt6sg",
  "venue": "ChemRxiv",
  "versions": []
}