Molecular Reconstruction with Stereochemical Relay: An Investigation into the Rearrangement of Spirodecadienone to Benzoxepane

Herein, we report the unusual skeletal rearrangement of spiro[4.5]decadienone to benzoxepane. In particular, Lewis acid‐promoted epoxide‐opening ipso‐cyclization of aryl epoxides afforded spiro[4.5]decadienone intermediates. Subsequent thermal activation assembled a benzoxepane core via rearomative...

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Bibliographic Details
Published in:Chemistry, an Asian journal an Asian journal, 2024-01, Vol.19 (2)
Main Authors: Sittihan, Satapanawat, Harada, Shingo, Isono, Tomohiro, Nemoto, Tetsuhiro, Ruchirawat, Somsak
Format: Article
Language:English
Subjects:
Chemistry
Lewis acid
Quinones
Stereoselectivity
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Summary:Herein, we report the unusual skeletal rearrangement of spiro[4.5]decadienone to benzoxepane. In particular, Lewis acid‐promoted epoxide‐opening ipso‐cyclization of aryl epoxides afforded spiro[4.5]decadienone intermediates. Subsequent thermal activation assembled a benzoxepane core via rearomative molecular reorganization. The sequence was high‐yielding and highly diastereoselective but sensitive to the aromatic substitution pattern and the epoxide side chain. Mechanistic studies suggested that the rearrangement proceeded via an uncommon intramolecular enolate attack onto the electrophilic O of p‐quinone oxonium zwitterion. DFT calculations helped rationalize the product distribution and the origin of diastereoselectivity. Initial investigation into the application of this chemical transformation is also presented.
ISSN:1861-4728
1861-471X
DOI:10.1002/asia.202300937