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
. 2012 May 18;14(10):2646-9.
doi: 10.1021/ol3010563. Epub 2012 May 9.

Studies toward the synthesis of the epoxykinamycin FL-120B': discovery of a decarbonylative photocyclization

Stephen S Scully  1 , John A Porco Jr
Affiliations

Studies toward the synthesis of the epoxykinamycin FL-120B': discovery of a decarbonylative photocyclization

Stephen S Scully et al. Org Lett. .

Abstract

Photo-Friedel-Crafts acylation of a naphthoquinone was attempted in an effort to access a diazobenzofluorenone en route to the epoxykinamycin natural product FL-120B'. Photoirradiation of the naphthoquinone substrate which resulted in the unexpected formation of a tetracyclic naphthofuran via a decarbonylative photocyclization process is described.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Synthetic approaches to kinamycin C and FL-120B'
Scheme 1
Scheme 1
Intermolecular Photo-Friedel-Crafts Acylation
Scheme 2
Scheme 2
Proposed Intramolecular Photo-Friedel-Crafts Acylation
Scheme 3
Scheme 3
Synthesis of Naphthoquinone 11
Scheme 4
Scheme 4
Unexpected Decarbonylative Photocyclization to 20
Scheme 5
Scheme 5
Synthesis and X-Ray Crystal Structure of 22 aYield determined by 1H NMR analysis using CH3NO2 as an internal standard.
Scheme 6
Scheme 6
Proposed Mechanism for Decarbonylative Photocyclization
Scheme 7
Scheme 7
Deuterium-Labelling Studies
Scheme 8
Scheme 8
Alternative Mechanism for Decarbonylative Photocyclization
See this image and copyright information in PMC

References

    1. Ito S, Matsuya T, Omura S, Otani M, Nakagawa A. J. Antibiot. 1970;23:315–317. - PubMed
    2. Hata T, Omura S, Iwai Y, Nakagawa A, Otani M. J. Antibiot. 1971;24:353–359. - PubMed
    3. Omura S, Nakagawa A, Yamada H, Hata T, Furusaki A. Chem. Pharm. Bull. 1973;21:931–940. - PubMed
    1. Lin HC, Chang SC, Wang NL, Chang LR. J. Antibiot. 1994;47:675–680. - PubMed
    2. Young J-J, Ho SN, Ju WM, Chang LR. J. Antibiot. 1994;47:681–687. - PubMed

    1. For a recent review including synthetic and mechanism-of-action studies of diazobenzofluorene natural products, see: Herzon SB, Woo CM. Nat. Prod. Rep. 2012;29:87–118.

    1. Lei X, Porco JA., Jr. J. Am. Chem. Soc. 2006;128:14790–14791. - PubMed
    2. Scully SS, Porco JA., Jr. Angew. Chem. Int. Ed. 2011;50:9722–9726. - PMC - PubMed

    1. For a recent example of serendipitous reaction discovery in studies toward diazobenzofluorene natural products, see: Baranczak A, Sulikowski GA. Org. Lett. 2012;14:1027–1029.

Publication types