Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2013 Jun 21;15(12):3098-101.
doi: 10.1021/ol401285d. Epub 2013 May 31.

A palladium-catalyzed carbo-oxygenation: the bielschowskysin case

Martin Himmelbauer  1 , Jean-Baptiste Farcet, Julien Gagnepain, Johann Mulzer
Affiliations

A palladium-catalyzed carbo-oxygenation: the bielschowskysin case

Martin Himmelbauer et al. Org Lett. .

Abstract

An asymmetric synthesis of an advanced tetracyclic intermediate toward the synthesis of bielschowskysin (1) is described. A biomimetic [2 + 2]-photocyclization was used to establish the cyclobutane core of bielschowskysin. Macrocyclization under Heck conditions led to an unprecedented carbo-oxygenation of a 1,1-disubstituted double bond.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1. Biosynthesis and Reported [2 + 2]-Approaches
Scheme 2
Scheme 2. Retrosynthetic Analysis
Scheme 3
Scheme 3. Preparation of the Allene Building Block
Scheme 4
Scheme 4. Preparation of the Coupling Partner
Scheme 5
Scheme 5. Fragment Coupling and [2 + 2]-Photocycloaddition
Scheme 6
Scheme 6. Preparation of Single Crystals for X-ray Analysis
Scheme 7
Scheme 7. Introduction of the Bromoallyl Appendage
Scheme 8
Scheme 8. Mechanistic Rationalization
Scheme 9
Scheme 9. Macrocyclization and Carbo-oxygenation
See this image and copyright information in PMC

References

    1. Marrero J.; Rodríguez A. D.; Baran P.; Raptis R. G.; Sanchez J. A.; Ortega-Barria E.; Capson T. L. Org. Lett. 2004, 6, 1661–1664. - PubMed
    1. Farcet J.-B.; Himmelbauer M.; Mulzer J. Org. Lett. 2012, 14, 2195–2197. - PubMed
    2. Farcet J.-B.; Himmelbauer M.; Mulzer J.. Eur. J. Org. Chem. 2013, accepted for publication
    1. Doroh B.; Sulikowski G. A. Org. Lett. 2006, 8, 903–906. - PMC - PubMed
    2. Miao R.; Gramani S. G.; Lear M. J. Tetrahedron Lett. 2009, 50, 1731–1733.
    3. Jana A.; Mondal S.; Md. Hossain F.; Ghosh S. Tetrahedron Lett. 2012, 53, 6830–6833.
    1. Nicolaou K. C.; Adsool V. A.; Hale C. R. H. Angew. Chem., Int. Ed. 2011, 50, 5149–5152. - PMC - PubMed
    2. Meyer M. E.; Phillips J. H.; Ferreira E. M.; Stoltz B. M. Tetrahedron 2013, 1–9. - PMC - PubMed
    1. Roethle P. A.; Trauner D. Org. Lett. 2006, 8, 345–347. - PubMed
    2. Roethle P. A.; Hernandez P. T.; Trauner D. Org. Lett. 2006, 8, 5901–5904. - PubMed
    3. Roethle P. A.; Trauner D. Nat. Prod. Rep. 2008, 8, 298–317. - PubMed

Publication types

LinkOut - more resources