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PreprintCC BY-NC-NDChemRxiv

An experimentally-validated principle for selectivity in endergonic reactions

  • Zhipeng Li1,2,3
  • Shuntaro Amano1,4
  • Shaymaa Al Shehimy1
  • Malak Rafieq Jaber1
  • Leonardo Andreoni5
  • Serena Silvi6
  • Zhong-Yuan Lu2,3
  • Giulio Ragazzon1
6 affiliations
  1. 1Institut de Science et d’Ingénierie Supramoléculaires (ISIS), University of Strasbourg, CNRS & iCFRC, UMR, 8 allée Gaspard, Strasbourg, France, 67000
  2. 2State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry
  3. 3Jilin University
  4. 4Department of Chemical Engineering, Delft University of Technology, Mekelweg 5, Delft, Netherlands, 2628
  5. 5Dipartimento di Chimica Industriale “Toso Montanari, Università di Bologna, via P. Gobetti 85, Bologna, Italy, I-40129
  6. 6Dipartimento di Chimica “G. Ciamician, Università di Bologna, via P. Gobetti 85, Bologna, Italy, I-40129
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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.

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Cite

BibTeXRIS
BibTeX
@misc{li2026experimentallyvalidated,
  title = {{An experimentally-validated principle for selectivity in endergonic reactions}},
  author = {Zhipeng Li and Shuntaro Amano and Shaymaa Al Shehimy and Malak Rafieq Jaber and Leonardo Andreoni and Serena Silvi and Zhong-Yuan Lu and Giulio Ragazzon},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010447/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010447/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - An experimentally-validated principle for selectivity in endergonic reactions
AU  - Zhipeng Li
AU  - Shuntaro Amano
AU  - Shaymaa Al Shehimy
AU  - Malak Rafieq Jaber
AU  - Leonardo Andreoni
AU  - Serena Silvi
AU  - Zhong-Yuan Lu
AU  - Giulio Ragazzon
PY  - 2026
DA  - 2026/10/14
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010447/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010447/v1
AB  - 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.
ER  -