Synlett 2021; 32(17): 1683-1701
DOI: 10.1055/a-1381-2881
account

Chemical Diversity of Volatile Macrocylic Lactones from Frogs

Stefan Schulz
,
Dennis Poth
,
Pardha Saradhi Peram
,
Susann Hötling
,
Markus Menke
,
Kristina Melnik
,
René Röpke
We thank the Deutsche Forschungsgemeinschaft for research grants (Grant No. SCHU 984/10-1 and SCHU 984/10-2).


Dedicated to the memory of Prof. Dr. Dr. h. c. mult. Wittko Francke

Abstract

For a long time, frogs were believed to communicate primarily via the acoustic channel, but during the last decades it became obvious that various lineages also use chemical communication. In this Account we present our research on the identification of volatile lactones from Madagascan Mantellidae and African Hyperoliidae frogs. Both possess male specific glands that can disseminate a range of volatile compounds. Key constituents are macrocyclic lactones. They show high variability in structure and occurrence. We focus here on the synthetic approaches we have used to clarify constitution and configuration of the glandular compounds. Key synthetic methods are ring-closing metathesis and nucleophilic epoxide opening. Often, but not always, the natural compounds occurs in amounts that excludes their investigation by NMR spectroscopy. Instead, we use GC/MS analysis, GC/IR, microreactions, and synthesis to identify such components. Several aspects of our work will be described giving some insight in our scientific approach.

1 Introduction

2 Macrocylic Lactones from the Fatty Acid Biosynthetic Pathway

3 Unsaturated Lactones

4 Terpenoid Lactones

5 Macrolide Occurrence

6 Conclusions



Publikationsverlauf

Eingereicht: 11. Januar 2021

Angenommen nach Revision: 02. Februar 2021

Accepted Manuscript online:
02. Februar 2021

Artikel online veröffentlicht:
23. Februar 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References

  • 1 Vieites DR, Wollenberg KC, Andreone F, Köhler J, Glaw F, Vences M. Proc. Natl. Acad. Sci. U.S.A. 2009; 106: 8267
  • 2 Vences M, Wahl-Boos G, Hoegg S, Glaw F, Spinelli Oliveira E, Meyer A, Perry S. Biol. J. Linn. Soc. 2007; 92: 529
  • 3 Poth D, Wollenberg KC, Vences M, Schulz S. Angew. Chem. Int. Ed. 2012; 51: 2187
  • 4 Garraffo HM, Caceres J, Daly JW, Spande FT, Andriamaharavo NR, Andriantsiferana M. J. Nat. Prod. 1993; 56: 1016
  • 5 Woodley SK. J. Comp. Physiol., A 2010; 196: 713
  • 6 Moore BP, Brown WV. Aust. J. Chem. 1976; 29: 1365
  • 7 Naoshima Y, Hasegawa H, Nishiyama T, Nakamura A. Bull. Chem. Soc. Jpn. 1989; 62: 608
  • 8 Bradshaw CW, Hummel W, Wong CH. J. Org. Chem. 1992; 57: 1532
  • 9 Chênevert R, Pelchat N, Morin P. Tetrahedron: Asymmetry 2009; 20: 1191
  • 10 van Lierop BJ, Lummis JA. M, Fogg DE. In Olefin Metathesis . Grela K. Wiley; Hoboken: 2014: 85
  • 11 Schulz S, Hötling S. Nat. Prod. Rep. 2015; 32: 1042
  • 12 Karlson P, Lüscher M. Nature 1959; 183: 55
  • 13 Kitahara T, Koseki K, Mori K. Agric. Biol. Chem. 1983; 47: 389
  • 14 Saporito RA, Spande TF, Garraffo HM, Donnelly MA. Heterocycles 2009; 79: 277
  • 15 Hantak MM, Grant T, Reinsch S, McGinnity D, Loring M, Toyooka N, Saporito RA. J. Chem. Ecol. 2013; 39: 1400
  • 16 Sanchez E, Rodríguez A, Grau JH, Lötters S, Künzel S, Saporito RA, Ringler E, Schulz S, Wollenberg Valero KC, Vences M. Genes 2019; 10: 733
  • 17 von Seebach M, Kozhushkov SI, Schill H, Frank D, Boese R, Benet-Buchholz J, Yufit DS, de Meijere A. Chem. Eur. J. 2007; 13: 167
  • 18 Hamanaka N, Kosuge S, Iguchi S. Synlett 1990; 139
  • 19 Inanaga J, Hirata K, Saeki H, Katsuki T, Yamaguchi M. Bull. Chem. Soc. Jpn. 1979; 52: 1989
  • 20 Nowack C, Peram PS, Wenzel S, Rakotoarison A, Glaw F, Poth D, Schulz S, Vences M. J. Zool. 2017; 303: 72
  • 21 Nowack C, Jordan S, Wittmer C. In Chemical Signals in Vertebrates 12 . East ML, Dehnhard M. Springer; New York: 2013: 37
  • 22 Pankevich DE, Baum MJ, Cherry JA. J. Neurosci. 2004; 24: 9451
  • 23 Poth D, Peram PS, Vences M, Schulz S. J. Nat. Prod. 2013; 76: 1548
  • 24 Rost D, Porta M, Gessler S, Blechert S. Tetrahedron Lett. 2008; 49: 5968
  • 25 Mori K. Tetrahedron 2008; 64: 4060
  • 26 Takle A, Kocieński P. Tetrahedron 1990; 46: 4503
  • 27 Peram PS, Vences M, Schulz S. Org. Biomol. Chem. 2017; 15: 6967
  • 28 U.S. Secretary of Commerce, 2017 NIST Chemistry WebBook (accessed Feb. 18, 2021): http://webbook.nist.gov/chemistry/name-ser.html#Top
  • 29 McLafferty FW. Wiley Registry of Mass Spectral Data, 12th ed., Wiley: Hoboken, 2020.
  • 30 Schulz S, Peram PS, Menke M, Hötling S, Röpke R, Melnik K, Poth D, Mann F, Henrichsen S, Dreyer K. J. Nat. Prod. 2017; 80: 2572
  • 31 Melnik K, Menke M, Rakotoarison A, Vences M, Schulz S. Org. Lett. 2019; 21: 2851
  • 32 Schroeter M, Weyerstahl P. Synth. Commun. 2004; 34: 1535
  • 33 Brown HC, Bhat KS. J. Am. Chem. Soc. 1986; 108: 5919
  • 34 Ghosh AK, Anderson DD. Org. Lett. 2012; 14: 4730
  • 35 Li N.-S, Piccirilli JA. Tetrahedron 2013; 69: 9633
  • 36 Starnberger I, Poth D, Peram PS, Schulz S, Vences M, Knudsen J, Barej MF, Rödel M.-O, Walzl M, Hödl W. Biol. J. Linn. Soc. 2013; 110: 828
  • 37 Millar JG, Pierce JrH. D, Pierce AM, Oehlschlager CA, Borden JH, Barak AV. J. Chem. Ecol. 1985; 11: 1053
  • 38 Millar JG, Pierce JrH. D, Pierce AM, Oehlschlager CA, Borden JH. J. Chem. Ecol. 1985; 11: 1071
  • 39 Oehlschlager AC, King GG. S, Pierce JrH. D, Pierce AM, Slessor KN, Millar JG, Borden HJ. J. Chem. Ecol. 1987; 13: 1543
  • 40 Jacobsen EN. Acc. Chem. Res. 2000; 33: 421
  • 41 Menke M, Peram PS, Starnberger I, Hödl W, Jongsma GF. M, Blackburn DC, Rödel M.-O, Vences M, Schulz S. Beilstein J. Org. Chem. 2016; 12: 2731
  • 42 Hong SH, Sanders DP, Lee CW, Grubbs RH. J. Am. Chem. Soc. 2005; 127: 17160
  • 43 Maynard HD, Grubbs RH. Tetrahedron Lett. 1999; 40: 4137
  • 44 Herbert MB, Grubbs RH. Angew. Chem. Int. Ed. 2015; 54: 5018
  • 45 Vanderwel D, Pierce HD. Jr, Oehlschlager AC, Borden JH, Pierce AM. Insect Biochem. 1990; 20: 567
  • 46 Vanderwel D, Johnston B, Oehlschlager AC. Insect Biochem. Molec. Biol. 1992; 22: 875
  • 47 Hötling S, Haberlag B, Tamm M, Collatz J, Mack P, Steidle JL. M, Vences M, Schulz S. Chem. Eur. J. 2014; 20: 3183
  • 48 Millar JG, Oehlschlager AC. J. Org. Chem. 1984; 49: 2332
  • 49 Ehrhorn H, Tamm M. Chem. Eur. J. 2019; 3190
  • 50 Micoine K, Persich P, Llaveria J, Lam M.-H, Maderna A, Loganzo F, Fürstner A. Chem. Eur. J. 2013; 19: 7370
  • 51 Willwacher J, Kausch-Busies N, Fürstner A. Angew. Chem. Int. Ed. 2012; 51: 12041
  • 52 Takahashi H, Kawakita T, Ohno M, Yoshioka M, Kobayashi S. Tetrahedron 1992; 48: 5691
  • 53 Haberlag B, Wu X, Brandhorst K, Grunenberg J, Daniliuc CG, Jones PG, Tamm M. Chem. Eur. J. 2010; 16: 8868
  • 54 Czyzewska E, Oehlschlager AC. In Studies in Natural Product Chemistry . Rahman A. Elsevier; Amsterdam: 1991: 219
  • 55 Hötling S, Bittner C, Tamm M, Dähn S, Collatz J, Steidle JL. M, Schulz S. Org. Lett. 2015; 17: 5004
  • 56 Haberlag B, Freytag M, Daniliuc CG, Jones PG, Tamm M. Angew. Chem. Int. Ed. 2012; 51: 13019
  • 57 Bates RW, Lu Y. J. Org. Chem. 2009; 74: 9460
  • 58 Stewart IC, Ung T, Pletnev AA, Berlin JM, Grubbs RH, Schrodi Y. Org. Lett. 2007; 9: 1589
  • 59 Lautens M, Colucci JT, Hiebert S, Smith ND, Bouchain G. Org. Lett. 2002; 4: 1879
  • 60 Corey EJ, Schmidt G. Tetrahedron Lett. 1979; 27: 399
  • 61 Govek SP, Overman LE. Tetrahedron 2007; 63: 8499
  • 62 Marino JP, McClure MS, Holub DP, Comasseto JV, Tucci FC. J. Am. Chem. Soc. 2002; 124: 1664
  • 63 Menke M, Melnik K, Peram PS, Starnberger I, Hödl W, Vences M, Schulz S. Eur. J. Org. Chem. 2018; 2651
  • 64 Weise CF, Pischl MC, Pfaltz A, Schneider C. J. Org. Chem. 2012; 77: 1477
  • 65 Corey EJ, Hua DH, Pan BC, Seitz SP. J. Am. Chem. Soc. 1982; 104: 6818
  • 66 Liedtke HC, Gower DJ, Wilkinson M, Gomez-Mestre I. Nat. Ecol. Evol. 2018; 2: 1792
  • 67 Sillam-Dussès D, Sémon E, Robert A, Bordereau C. Chemoecology 2009; 19: 103
  • 68 Matsumura F, Coppel HC, Tai A. Nature 1968; 219: 963
  • 69 Schlawis C, Kern S, Kudo Y, Grunenberg J, Moore BS, Schulz S. Angew. Chem. Int. Ed. 2018; 57: 14921
  • 70 Fürstner A. Angew. Chem. Int. Ed. 2013; 52: 2794
  • 71 Daly JW, Spande TF, Garraffo HM. J. Nat. Prod. 2005; 68: 1556
  • 72 Daly JW, Garraffo HM, Spande TF, Giddings L.-A, Saporito RA, Vieites DR, Vences M. J. Chem. Ecol. 2008; 252
  • 73 Glaw F, Vences M. A Field Guide to the Amphibians and Reptiles of Madagascar. Vences & Glaw; Cologne: 2007
  • 74 Bletz MC, Bunk B, Spröer C, Biwer P, Reiter S, Rabemananjara FC. E, Schulz S, Overmann J, Vences M. PLoS One 2019; 14: e0223747
  • 75 Vences M, Hildenbrand A, Warmuth KM, Andreone F, Glaw F. Zootaxa 2018; 4486: 575