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Peer-reviewedCC BYJournal of the American Chemical Society

Catalytic Asymmetric Hydration of Alkenes

  • Hibiki HATANO1
  • Vitor Alcantara Fernandes2
  • Subrata Mukherjee2
  • Chendan Zhu3
  • Akito Takahira1
  • Pingyu Jiang2
  • Mingoo Jin2
  • Yu Harabuchi2
  • Ruben Staub2
  • Min Gao2
  • Alexandre A. Varnek2,4
  • Satoshi MAEDA2
2 more authors
  • Nobuya Tsuji2
  • Benjamin List2,3
4 affiliations
  1. 1Hokkaido University , , , ,
  2. 2Hokkaido University , , ,
  3. 3Max-Planck-Institut für Kohlenforschung , ,
  4. 4University of Strasbourg , , ,
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Abstract

The asymmetric Markovnikov hydration of alkenes to alcohols, transforming abundant feedstock chemicals and water into synthetically versatile building blocks, has long remained inaccessible. The reaction is inherently reversible because of unfavorable entropy, preventing asymmetric induction. While lowering the temperature should favor product formation in principle, such conditions are normally incompatible with the required protonation of simple alkenes and with maintaining a homogeneous reaction mixture. Here we show that this long-standing limitation is overcome by making catalytic activity viable under cryogenic conditions. Using confined strong Bro̷nsted acid catalysts and solvent-organized hydrogen-bonding networks that facilitate protonation of otherwise unreactive alkenes, we achieve a highly enantioselective hydration of electronically neutral alkenes with water. This thermodynamic temperature dependence also allows conversion of racemic tertiary alcohols into enantioenriched forms through a one-pot formal deracemization. Experimental and computational studies indicate that perfluorinated solvents form extended hydrogen-bonding networks that enhance both reactivity and stereocontrol. These findings establish a general strategy for overcoming fundamental constraints imposed by reversibility.

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Cite

BibTeXRIS
BibTeX
@article{hatano2026catalytic,
  title = {{Catalytic Asymmetric Hydration of Alkenes}},
  author = {Hibiki HATANO and Vitor Alcantara Fernandes and Subrata Mukherjee and Chendan Zhu and Akito Takahira and Pingyu Jiang and Mingoo Jin and Yu Harabuchi and Ruben Staub and Min Gao and Alexandre A. Varnek and Satoshi MAEDA and Nobuya Tsuji and Benjamin List},
  journal = {Journal of the American Chemical Society},
  year = {2026},
  month = jun,
  doi = {10.1021/jacs.6c06916},
  url = {https://doi.org/10.1021/jacs.6c06916},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Catalytic Asymmetric Hydration of Alkenes
AU  - Hibiki HATANO
AU  - Vitor Alcantara Fernandes
AU  - Subrata Mukherjee
AU  - Chendan Zhu
AU  - Akito Takahira
AU  - Pingyu Jiang
AU  - Mingoo Jin
AU  - Yu Harabuchi
AU  - Ruben Staub
AU  - Min Gao
AU  - Alexandre A. Varnek
AU  - Satoshi MAEDA
AU  - Nobuya Tsuji
AU  - Benjamin List
PY  - 2026
DA  - 2026/06/02
JO  - Journal of the American Chemical Society
DO  - 10.1021/jacs.6c06916
UR  - https://doi.org/10.1021/jacs.6c06916
AB  - The asymmetric Markovnikov hydration of alkenes to alcohols, transforming abundant feedstock chemicals and water into synthetically versatile building blocks, has long remained inaccessible. The reaction is inherently reversible because of unfavorable entropy, preventing asymmetric induction. While lowering the temperature should favor product formation in principle, such conditions are normally incompatible with the required protonation of simple alkenes and with maintaining a homogeneous reaction mixture. Here we show that this long-standing limitation is overcome by making catalytic activity viable under cryogenic conditions. Using confined strong Bro̷nsted acid catalysts and solvent-organized hydrogen-bonding networks that facilitate protonation of otherwise unreactive alkenes, we achieve a highly enantioselective hydration of electronically neutral alkenes with water. This thermodynamic temperature dependence also allows conversion of racemic tertiary alcohols into enantioenriched forms through a one-pot formal deracemization. Experimental and computational studies indicate that perfluorinated solvents form extended hydrogen-bonding networks that enhance both reactivity and stereocontrol. These findings establish a general strategy for overcoming fundamental constraints imposed by reversibility.
SN  - 0002-7863
SN  - 1520-5126
SN  - 1943-2984
ER  -