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
. 2017 May 26;80(5):1558-1562.
doi: 10.1021/acs.jnatprod.7b00082. Epub 2017 Apr 11.

Structural Reassignment and Absolute Stereochemistry of Madurastatin C1 (MBJ-0034) and the Related Aziridine Siderophores: Madurastatins A1, B1, and MBJ-0035

Andrew R Tyler, Hamed Mosaei, Stephanie Morton, Paul G Waddell, Corinne Wills, William McFarlane, Joe Gray, Michael Goodfellow, Jeff Errington  1 , Nick Allenby  1 , Nikolay Zenkin, Michael J Hall
Affiliations

Structural Reassignment and Absolute Stereochemistry of Madurastatin C1 (MBJ-0034) and the Related Aziridine Siderophores: Madurastatins A1, B1, and MBJ-0035

Andrew R Tyler et al. J Nat Prod. .

Abstract

The madurastatins are pentapeptide siderophores originally described as containing an unusual salicylate-capped N-terminal aziridine ring. Isolation of madurastatin C1 (1) (also designated MBJ-0034), from Actinomadura sp. DEM31376 (itself isolated from a deep sea sediment), prompted structural reevaluation of the madurastatin siderophores, in line with the recent work of Thorson and Shaaban. NMR spectroscopy in combination with partial synthesis allowed confirmation of the structure of madurastatin C1 (1) as containing an N-terminal 2-(2-hydroxyphenyl)oxazoline in place of the originally postulated aziridine, while absolute stereochemistry was determined via Harada's advanced Marfey's method. Therefore, this work further supports Thorson and Shaaban's proposed structural revision of the madurastatin class of siderophores (madurastatins A1 (2), B1 (3), C1 (1), and MBJ-0036 (4)) as N-terminal 2-(2-hydroxyphenyl)oxazolines.

PubMed Disclaimer

Conflict of interest statement

Notes

The authors declare no competing financial interest

Figures

Figure 1
Figure 1
Previously proposed structures of the “aziridine” containing madurastatin siderophores
Figure 2
Figure 2
(a) Scanning electron micrograph of strain DEM31376 showing spiral chains of warty ornamented spores following growth on ISP3 agar, bar indicates 2 μm. (b) Neighbor-joining tree based on nearly complete 16S rRNA gene sequences showing relationships between strain DEM31376 and closely related type strains of Actinomadura species. Asterisks indicate branches also recovered using maximum likelihood and maximum parsimony tree making methods. Numbers at nodes indicate bootstrap values based on neighbor joining analysis of 1000 resampled datasets.
Figure 3
Figure 3
Revised structure of madurastatin C1 (1) including absolute stereochemistry.
Scheme 1
Scheme 1
(i) MsCl, Et3N, DCM, 0 °C to RT, 18 h, then Et3N, THF, reflux, 16 h, 70%. (ii) Et3SiH, Et3N, DCM, 0 °C to RT, 5 h. (iii) 2-(benzyloxy)benzoyl chloride, Et3N, -78 °C to RT, 48 h, 35% over 2 steps.
Scheme 2
Scheme 2
(i) 2-(benzyloxy)benzoyl chloride, Et3N, -78 °C to RT, 18 h, 95%. (ii) DCM, DAST, -78 °C to RT, 2 h, 79%.
See this image and copyright information in PMC

References

    1. Hider RC, Konga X. Nat Prod Rep. 2010;27:637–657. - PubMed
    1. Miethke M, Marahiel MA. Microbiol Mol Biol Rev. 2007;71:413–451. - PMC - PubMed
    1. Trujillo ME, Goodfellow M. In: Actinomadura. Bergey's Manual of Systematics of Archaea and Bacteria; Lechevalier and Lechevalier, 400AL emend. Stackebrandt, Goodfellow, editors. Kroppenstedt: John Wiley & Sons, Inc., in association with Bergey's Manual Trust; 2015. pp. 1–32. 156.
    1. Gerber NN. Tetrahedron Lett. 1970;11:809–812. - PubMed
    2. Zein N, Solomon W, Colson KL, Schroeder DR. Biochemistry. 1995;34:11591–11597. - PubMed
    3. Simmons L, Kaufmann K, Garcia R, Schwär G, Huch V, Müller R. Bioorg Med Chem. 2011;19:6570–6575. - PubMed
    4. Wyche TP, Piotrowski JS, Hou Y, Braun D, Deshpande R, McIlwain S, Ong IM, Myers CL, Guzei IA, Westler WM, Andes DR, et al. Angew Chem Int Ed. 2014;53:11583–11586. - PMC - PubMed
    5. Shaaban KA, Elshahawi SI, Wang X, Horn J, Kharel MK, Leggas M, Thorson JS. J Nat Prod. 2015;78:1723–1729. - PMC - PubMed
    6. Shin B, Kim B-Y, Cho E, Oh K-B, Shin J, Goodfellow M, Oh D-C. J Nat Prod. 2016;79:1886–1890. - PubMed
    7. Kimura T, Iwatsuki M, Asami Y, Ishiyama A, Hokari R, Otoguro K, Matsumoto A, Sato N, Shiomi K, Takahashi Y, Ōmura S, et al. J Antibiot. 2016;69:818–824. - PubMed
    8. Kodani S, Komaki H, Ishimura S, Hemmi H, Ohnishi-Kameyama M. J Ind Microbiol Biot. 2016;43:1159–1165. - PubMed
    1. Harada K, Tomita K, Fujii K, Masuda K, Mikami Y, Yazawa K, Komaki H. J Antibiot. 2004;57:125–135. - PubMed
    2. Mazzei E, Iorio M, Maffioli SI, Sosio M, Donadio S. J Antibiot. 2012;65:267–269. - PubMed
    3. Kawahara T, Itoh M, Izumikawa M, Sakata N, Tsuchida T, Shin-ya K. J Antibiot. 2014;67:577–580. - PubMed

Publication types

LinkOut - more resources