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

Year: 2026

Type: preprint

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.

Source: ChemRxiv

DOI: 10.26434/chemrxiv.15010075/v1

Authors: Kenichi Kato, Nagisa Kawabata, Yori Kajiwara, Tatsuya Nishimura, Katsuhiro Maeda, Shunsuke Ohtani, Tomoki Ogoshi

Institutions: Kyoto University, Kanazawa University, Nano Life Science Institute, Kanazawa University

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Ministry of Education, Culture, Sports, Science and Technology, Japan Society for the Promotion of Science

Award: G8748989930

OpenAlex ID: W7221000728

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