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Published April 8, 2020 | Supplemental Material
Journal Article Open

SeO₂-Mediated Oxidative Transposition of Pauson–Khand Products

Abstract

Oxidative transpositions of bicyclic cyclopentenones mediated by selenium dioxide (SeO₂) are disclosed. Treatment of Pauson–Khand reaction (PKR) products with SeO₂ in the presence or absence of water furnishes di- and trioxidized cyclopentenones, respectively. Mechanistic investigations reveal multiple competing oxidation pathways that depend on substrate identity and water concentration. Functionalization of the oxidized products via cross-coupling methods demonstrates their synthetic utility. These transformations allow rapid access to oxidatively transposed cyclopentenones from simple PKR products.

Additional Information

© 2020 American Chemical Society. Received: January 9, 2020; Published: March 19, 2020. We thank Dr. M. Takase and L. Henling (both of Caltech) for X-ray data collection and Dr. J. Hofstra (Caltech) for X-ray data refinement. Dr. S. Virgil and the Caltech Center for Catalysis and Chemical Synthesis are gratefully acknowledged for access to analytical equipment. Fellowship support was provided by the NSF (S.E.D., M.R.M. Grant No. DGE-1144469). S.E.R. is a Heritage Medical Research Institute Investigator. Financial support from the NIH (R35GM118191-01) is acknowledged. Author Contributions: S.E.D. and M.R.R. contributed equally to this work. The authors declare no competing financial interest. The X-ray crystal structure data for compound 15e was submitted to the Cambridge Crystallographic Data Center, No. 1970101.

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Created:
August 19, 2023
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October 19, 2023