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SeO₂-Mediated Oxidative Transposition of Pauson–Khand Products

Dibrell, Sara E. and Maser, Michael R. and Reisman, Sarah E. (2020) SeO₂-Mediated Oxidative Transposition of Pauson–Khand Products. Journal of the American Chemical Society, 142 (14). pp. 6483-6487. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20200319-125552181

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.9b13818DOIArticle
ORCID:
AuthorORCID
Dibrell, Sara E.0000-0003-0332-1101
Reisman, Sarah E.0000-0001-8244-9300
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.
Group:Heritage Medical Research Institute
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1144469
Heritage Medical Research InstituteUNSPECIFIED
NIHR35GM118191-01
Issue or Number:14
Record Number:CaltechAUTHORS:20200319-125552181
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200319-125552181
Official Citation:SeO2-Mediated Oxidative Transposition of Pauson–Khand Products. Sara E. Dibrell, Michael R. Maser, and Sarah E. Reisman. Journal of the American Chemical Society 2020 142 (14), 6483-6487; DOI: 10.1021/jacs.9b13818
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:102000
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 Mar 2020 20:03
Last Modified:20 Aug 2020 20:34

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