When π–π Stacking Outcompetes Hydrogen Bonding: Pre-Reactive Intermediates in the Furan–Acrolein Diels–Alder Reaction
This study presents the experimental characterization of pre-reactive intermediates in the furan-acrolein Diels-Alder reaction using high-resolution rotational spectroscopy. Three distinct isomers were identified, with π-π stacking unexpectedly prevailing over hydrogen-bonded structures, and the <i>exo</i> structure being slightly more stable than <i>endo</i>. The computationally affordable yet accurate XYG3 method, validated against benchmark CCSD(T) calculations, accurately reproduced the energetic ordering of the isomers. Solvent effects were investigated through microsolvation models, revealing that hexafluoro-2-propanol preserves π-π stacking and enhances <i>exo</i> selectivity via strong hydrogen-bond networks. These findings provide molecular-level insights into the stereocontrol of Diels-Alder reactions, outlining a generalizable role of π-π stacking and solvent-induced noncovalent forces in determining stereoselectivity in solution.
Authors
- Gang Fu (ORCID: https://orcid.org/0000-0001-8060-4215)
- Walther Camináti (ORCID: https://orcid.org/0000-0002-1845-3759)
- Xiao Tian (ORCID: https://orcid.org/0000-0002-8825-0885)
- Wenping Guo (ORCID: https://orcid.org/0000-0001-7553-0645)
- Xiaodong Wen (ORCID: https://orcid.org/0000-0001-5626-8581)
- Xingwu Liu (ORCID: https://orcid.org/0000-0002-8564-1151)
- Qian Gou (ORCID: https://orcid.org/0000-0003-3831-3582)
- Hao Wang (ORCID: https://orcid.org/0000-0002-9131-0199)
- Xingchen Liu (ORCID: https://orcid.org/0000-0002-9704-5728)
- Li Yang (ORCID: https://orcid.org/0000-0002-0143-3524)
- Jiaxu Zhang (ORCID: https://orcid.org/0000-0002-3125-7824)
- Yuwei Zhou (ORCID: https://orcid.org/0000-0001-9582-7331)
Institutions
- Chongqing University (CN)
- Harbin Institute of Technology (CN)
- National Energy Research Center (JO)
- Institute of Coal Chemistry (CN)
- State Key Laboratory of Coal Conversion
- Ministry of Industry and Information Technology (CN)
- University of Bologna (IT)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-08-21
- DOI
- https://doi.org/10.1021/jacs.5c08596
- Citations
- 5
- Primary Topic
- Asymmetric Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 4.68
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences
- National Key Research and Development Program of China
- Fundamental Research Funds for the Central Universities
- National Science Fund for Distinguished Young Scholars