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PreprintCC BY-NC-NDChemRxiv

Chirality Relay via Non-stereogenic Carbocations: from Stereogenic Alcohol to Twisted Tricyclic Skeleton

  • Kenichi Kato1,2
  • Nagisa Kawabata1
  • Yori Kajiwara2
  • Tatsuya Nishimura3
  • Katsuhiro Maeda3,4
  • Shunsuke Ohtani1,2
  • Tomoki Ogoshi1,2,4
4 affiliations
  1. 1Department of Chemical Science and Engineering, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, Japan, 615-8510
  2. 2Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, Japan, 615-8510
  3. 3Division of Material Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Japan, 920-1192
  4. 4WPI Nano Life Science Institute, Kanazawa University, Kakuma-machi, Kanazawa, Japan, 920-1192
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Abstract

Stereogenic carbon loses its stereochemistry when it is converted into planar carbocation. Retention of the chirality is difficult unless static reference chirality is introduced within reactant to change the reactions diastereoselective. Herein we report a rare reaction in which a stereogenic alcohol gives a chiral twisted tricyclic skeleton by acid-mediated dehydrative cyclization. The intermediates are carbocations without any stereogenic centers, and their non-stereogenic conformational features relay the chiral information to the product. The chiral twist is computed to be flexible in the alcohol reactant and initial carbocation intermediate, but it is induced through the reaction steps to acquire thermal robustness. This chirality relay also provides an effective synthetic method for each enantiomer of the product, which is a valuable intrinsically chiral building block.

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Cite

BibTeXRIS
BibTeX
@misc{kato2026chirality,
  title = {{Chirality Relay via Non-stereogenic Carbocations: from Stereogenic Alcohol to Twisted Tricyclic Skeleton}},
  author = {Kenichi Kato and Nagisa Kawabata and Yori Kajiwara and Tatsuya Nishimura and Katsuhiro Maeda and Shunsuke Ohtani and Tomoki Ogoshi},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010075/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010075/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Chirality Relay via Non-stereogenic Carbocations: from Stereogenic Alcohol to Twisted Tricyclic Skeleton
AU  - Kenichi Kato
AU  - Nagisa Kawabata
AU  - Yori Kajiwara
AU  - Tatsuya Nishimura
AU  - Katsuhiro Maeda
AU  - Shunsuke Ohtani
AU  - Tomoki Ogoshi
PY  - 2026
DA  - 2026/10/08
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010075/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010075/v1
AB  - Stereogenic carbon loses its stereochemistry when it is converted into planar carbocation. Retention of the chirality is difficult unless static reference chirality is introduced within reactant to change the reactions diastereoselective. Herein we report a rare reaction in which a stereogenic alcohol gives a chiral twisted tricyclic skeleton by acid-mediated dehydrative cyclization. The intermediates are carbocations without any stereogenic centers, and their non-stereogenic conformational features relay the chiral information to the product. The chiral twist is computed to be flexible in the alcohol reactant and initial carbocation intermediate, but it is induced through the reaction steps to acquire thermal robustness. This chirality relay also provides an effective synthetic method for each enantiomer of the product, which is a valuable intrinsically chiral building block.
ER  -