Polyazamacrolides from ladybird beetles: ring-size selective oligomerization

The pupal defensive secretion of the 24-pointed ladybird beetle, Subcoccinella vigintiquatuorpunctata, consists of a mixture of macrocyclic polyamines, dominated by the three dimeric, 30-membered macrocycles 11-13, derived from the two building blocks 11-(2-hydoxyethylamino)-5-tetradecenoic acid (9)...

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Bibliographic Details
Published in:Proceedings of the National Academy of Sciences - PNAS 1998-11, Vol.95 (23), p.13387-13391
Main Authors: Schroeder, F.C. (Baker Laboratory, Cornell University, Ithaca, NY.), Smedley, S.R, Gibbons, L.K, Farmer, J.J, Attygalle, A.B, Eisner, T, Meinwald, J
Format: Article
Language:English
Subjects:
ALCALOIDE
ALCALOIDES
ALKALOIDS
Alkaloids - chemistry
ALLOMONE
ALLOMONES
ALOMONAS
Amino acids
Animals
Beetles
CHEMICAL STRUCTURE
CHEMISTRY
CHIMIE
COCCINELLIDAE
Coleoptera - chemistry
DEFENSIVE SECRETIONS
Dimerization
Dimers
ESPECTROSCOPIA RMN
ESTRUCTURA QUIMICA
Fatty Acids, Unsaturated - chemistry
Hair
Hydroxy acids
Insects
Ions
Isomers
Lactones
NMR SPECTROSCOPY
Physical Sciences
POLIAMINAS
POLYAMINE
POLYAMINES
PUPAE
PUPAS
PUPE
QUIMICA
Secretion
SPECTROSCOPIE RMN
STEREOCHEMISTRY
STRUCTURE CHIMIQUE
SUBCOCCINELLA VIGINTIQUATTUORPUNCTATA
Subcoccinella vigintiquatuorpunctata
Trimers
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Summary:The pupal defensive secretion of the 24-pointed ladybird beetle, Subcoccinella vigintiquatuorpunctata, consists of a mixture of macrocyclic polyamines, dominated by the three dimeric, 30-membered macrocycles 11-13, derived from the two building blocks 11-(2-hydoxyethylamino)-5-tetradecenoic acid (9) and 11-(2-hydoxyethylamino)-5,8-tetradecadienoic acid (10). Smaller amounts of the four possible cyclic trimers of 9 and 10 were also detected, corresponding to 45-membered macrocycles. Structural assignments were based on NMR-spectroscopic investigations and HPLC-MS analyses. In addition, the all-S absolute configuration of the S. vigintiquatuatuorpunctata macrocycles was determined by comparison of derivatives of the natural material with enantiomerically pure synthetic samples. Comparing this alkaloid mixture with that of the pupal defensive secretion in related ladybird beetle species indicates that the degree of oligomerization of the 2-hydroxyethylamino carboxylic acid building blocks can be carefully controlled by the insects
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.95.23.13387