Skip to content
DraconiticResearch
Search Sources API
197,785 studies31 sourcesUpdated 7 min ago
PreprintCC BYChemRxiv

Transition state to minimum conversion in the Cope rearrangement under gigapascal pressure

  • Jorge Laranjeira1
  • Roberto Cammi2
  • Bo Chen1,3,4,5
5 affiliations
  1. 1Donostia International Physics Center, Paseo Manuel de Lardizabal 4, Donostia-San Sebastian, Spain, 20018
  2. 2Dipartimento di Scienze Chimiche, della Vita e della Sostenibilitá Ambientale, Università degli Studi di Parma, Parco Area delle Scienze 11/a, Parma, Italy, 43124
  3. 3IKERBASQUE, Basque Foundation for Science, Plaza Euskadi 5, Bilbao, Spain, 48009
  4. 4Departamento de Química Orgánica I, Facultad de Química/Kimika Fakultatea
  5. 5Universidad del País Vasco/Euskal Herriko Unibertsitatea (UPV/EHU
Open at sourcePDFDOICite

Abstract

Converting a transition state (TS) into a minimum is a challenging, yet possible, task, commonly achievable via chemical substitution. Pressure is expected to favor TSs that correspond to volume minima, yet experimentally or computationally demonstrated TS-to-minimum conversions remain rare. Here, we demonstrate a pressure-induced TS-to-minimum conversion in the Cope rearrangement at ∼18 GPa. Extreme pressure polarizable continuum model (XP-PCM) optimizations and vibrational analyses reveal the gradual conversion of the TS imaginary mode into a real vibrational mode. Helium compression chamber (HeCC) simulations unveil a pressure-driven inversion of the reaction-path curvature at the TS in the Gibbs free energy profile. Cyano substitution produces effects on bond distances and vibrational frequencies similar to those induced by pressure, highlighting parallels between chemical and mechanical stabilization. Although compression also accelarates the open-shell pathway, the closed-shell pathway remains thermodynamically favored up to 31 GPa. These findings highlight pressure as a powerful means of reshaping reaction landscapes, effectively enabling new chemistry.

Related

  1. Constant-Pressure Atmosphere Engineering Induced δ-α Phase Transition in FAPbI3 Single Crystal for X-Ray Detection
    Gang Jin, Guangya Zheng, Xiaoqing Liu +6
    Advanced Optical MaterialsPeer-reviewedCC BY-NC 4.0Full textMaterials & polymersHAL
  2. Investigation of α-Silylalcohols as Chiral Umpolung Carbanion Surrogates through Stereospecific 1,2-Brook Rearrangement
    TyAnn McHenry, Joshua D. Sieber
    ChemRxivPreprintLicence not stated1 citedGeneral chemistryChemRxiv
  3. Direct Access to α-Aryl-β-Amino Aldehydes via Hypervalent Iodine-Mediated Oxidative Rearrangement of Cinnamyl Amines
    Ali Mubarik, Jin Hang Tang, Hongyu Zhong
    ChemRxivPreprintLicence not statedGeneral chemistryChemRxiv
  4. Lewis Acid Catalyzed Cyclizative Rearrangement Strategy for One-Step 3-SF5- Furoquinoline and Furopyridine Synthesis
    Cailu Yue, Xiaoyan Li, Jiashuo Zhang +2
    ChemRxivPreprintLicence not statedGeneral chemistryChemRxiv
  5. Remote N‑Substituent‑Tuned Dichotomous Diradical Scission Enables Photocatalytic Divergent Rearrangement of Allylic Aminophosphines
    Peng-Fei Zhao, Zuo-Shuai Wang, Hao Chen +2
    ChemRxivPreprintLicence not statedGeneral chemistryChemRxiv

Cite

BibTeXRIS
BibTeX
@misc{laranjeira2026transition,
  title = {{Transition state to minimum conversion in the Cope rearrangement under gigapascal pressure}},
  author = {Jorge Laranjeira and Roberto Cammi and Bo Chen},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010501/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010501/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Transition state to minimum conversion in the Cope rearrangement under gigapascal pressure
AU  - Jorge Laranjeira
AU  - Roberto Cammi
AU  - Bo Chen
PY  - 2026
DA  - 2026/10/15
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010501/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010501/v1
AB  - Converting a transition state (TS) into a minimum is a challenging, yet possible, task, commonly achievable via chemical substitution. Pressure is expected to favor TSs that correspond to volume minima, yet experimentally or computationally demonstrated TS-to-minimum conversions remain rare. Here, we demonstrate a pressure-induced TS-to-minimum conversion in the Cope rearrangement at ∼18 GPa. Extreme pressure polarizable continuum model (XP-PCM) optimizations and vibrational analyses reveal the gradual conversion of the TS imaginary mode into a real vibrational mode. Helium compression chamber (HeCC) simulations unveil a pressure-driven inversion of the reaction-path curvature at the TS in the Gibbs free energy profile. Cyano substitution produces effects on bond distances and vibrational frequencies similar to those induced by pressure, highlighting parallels between chemical and mechanical stabilization. Although compression also accelarates the open-shell pathway, the closed-shell pathway remains thermodynamically favored up to 31 GPa. These findings highlight pressure as a powerful means of reshaping reaction landscapes, effectively enabling new chemistry.
ER  -