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Published April 8, 2020 | Version Supplemental Material
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SeO₂-Mediated Oxidative Transposition of Pauson–Khand Products

Creators

  • 1. ROR icon California Institute of Technology

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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Supplemental Material - ja9b13818_si_001.pdf

Supplemental Material - ja9b13818_si_002.zip

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Additional details

Identifiers

Eprint ID
102000
Resolver ID
CaltechAUTHORS:20200319-125552181

Funding

NSF Graduate Research Fellowship
DGE-1144469
Heritage Medical Research Institute
NIH
R35GM118191-01

Dates

Created
2020-03-19
Created from EPrint's datestamp field
Updated
2021-11-16
Created from EPrint's last_modified field

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Caltech groups
Heritage Medical Research Institute