Stereocontrolled Formation of Three Contiguous Stereogenic Centers by Free Radical Cyclization – Synthesis of (+)‐Iridomyrmecin and (–)‐Iso‐iridomyrmecin – Formal Synthesis of δ‐Skythantine

Schöllhorn, Bernd; Mulzer, Johann

doi:10.1002/ejoc.200500711

Cited by 13 publications

(2 citation statements)

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“…These samples were found to have spectral characteristics entirely consistent with those reported for the natural products (Schöllhorn and Mulzer, 2006;Beckett et al, 2010).…”

Section: Methodssupporting

confidence: 72%

Stereoselective Chemical Defense in the Drosophila Parasitoid Leptopilina heterotoma is Mediated by (−)-Iridomyrmecin and (+)-Isoiridomyrmecin

et al. 2012

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Chemical defense mechanisms are widespread among insects but have rarely been demonstrated in parasitoid wasps. Here, we show that the Drosophila parasitoid Leptopilina heterotoma (Hymenoptera, Figitidae) produces (−)-iridomyrmecin and (+)-isoiridomyrmecin in a cephalic gland, and that these chemicals have a highly repellent effect on ants. Stereoselective synthesis of 4 stereoisomers of iridomyrmecin allowed us to demonstrate that the repellent effect of iridomyrmecins depends on the stereochemistry. Potential food items impregnated with natural doses of (−)-iridomyrmecin were avoided by ants much longer than those impregnated with (+)-iridomyrmecin, (+)-isoiridomyrmecin, or (−)-isoiridomyrmecin, respectively. Quantitative headspace analyses revealed furthermore that females and males of L. heterotoma released iridomyrmecins in higher amounts when confronted with ants. This is the first time, that (−)-iridomyrmecin and (+)-isoiridomyrmecin are reported as natural products. Females synthesize more iridomyrmecins than males, and the most active (−)-iridomyrmecin is produced by females only. We, therefore, hypothesize that this defense mechanism is used mainly by female wasps when foraging for Drosophila larvae on rotten fruits, but also may protect male wasps during dispersal.

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“…These samples were found to have spectral characteristics entirely consistent with those reported for the natural products (Schöllhorn and Mulzer, 2006;Beckett et al, 2010).…”

Section: Methodssupporting

confidence: 72%

Stereoselective Chemical Defense in the Drosophila Parasitoid Leptopilina heterotoma is Mediated by (−)-Iridomyrmecin and (+)-Isoiridomyrmecin

et al. 2012

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“…Although 1 and 2 have been known for some time and prepared using a diversity of synthetic approaches, we took this opportunity to continue our work on the divergent diastereoselective synthesis of iridoids using citronellol or citronellal as starting materials . A preliminary description of our synthetic approach to 1 and 2 was reported with a study of their role in the chemical ecology of L.…”

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confidence: 99%

Divergent Diastereoselective Synthesis of Iridomyrmecin, Isoiridomyrmecin, Teucrimulactone, and Dolicholactone from Citronellol

2013

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Alkaloids

Mascavage

Jasmin

Sonnet

et al. 2010

Ullmann's Encyclopedia of Industrial Chemistry

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The article contains sections titled: 1. Introduction 2. Alkaloids Derived from Polyketides and the Amino Acids Ornithine and Lysine 2.1. Alkaloids Derived by the Insertion of Nitrogen into a Polyketide 2.1.1. ( S )‐(+)‐Coniine, γ‐Coniceine and Related Alkaloids 2.1.2. Solenopsin Family (Fire Ant Alkaloids) 2.1.3. Perhydroazaphenalenes: Defensive Alkaloids of the Coccinellidae 2.1.4. Cyanobacteria Alkaloids 2.1.5. Additional Polyketide‐Derived Alkaloids 2.2. Alkaloids Derived from Ornithine and/or Arginine 2.2.1. Tropane Alkaloids 2.2.2. Pyrrolizidine Alkaloids 2.3. Alkaloids Derived from Ornithine (and/or Arginine) and Nicotinic Acid 2.4. Alkaloids Derived from Lysine (Lys, K) and Nicotinic Acid 2.5. Purine Alkaloids 2.6. Imidazole Alkaloids 2.7. Pepper Alkaloids 3. Alkaloids Derived from the Shikimate Pathway 3.1. Alkaloids Derived from Anthranilate 3.2. Alkaloids Derived from Phenylalanine and Tyrosine 3.2.1. Biosynthesis of Dopamine, Mescaline and Capsaicin 3.2.2. Biosynthesis of Tetrahydroisoquinoline Alkaloids 3.2.3. Cryptostyline (Orchidaceae) and Alkaloids of the Amaryllidaceae 3.2.4. Ephedra Alkaloids 3.3. Alkaloids Derived from Tyrosine 3.4. Alkaloids Derived from Tryptophan and/or Tryptamine (Indole Alkaloids) 3.4.1. Alkaloids Derived from Tryptamine and an Unrearranged Monoterpene Unit 3.4.2. Mold Metabolites 3.4.3. Ergot Alkaloids 3.4.4. Corynantheine–Heteroyohimbine Structural Types 3.4.5. Corynantheine‐Type Alkaloids 3.4.6. Ajmalicine‐Type Alkaloids 3.4.7. Heteroyohimbine Oxindole Type 3.4.8. Glucoalkaloids 3.4.9. Yohimbine–Reserpine Structural Types 3.4.10. Akuammidine–Quebrachidine–Ervatamine–Gelsemine–Akuammiline Structural Types 3.4.11. Uleine–Ellipticine–Vallesamine–Ngouniensine Structural Types 3.5. The Cinchona Structural Type 3.6. The Camptothecin Structural Type 3.7. Terpene, Sesquiterpene, Diterpene and Steroidal Alkaloids (→ ((anchor interlink a26_205.xml Terpenes))) 3.7.1. Overview of Terpenoid Biosynthesis 3.7.2. Monoterpene Alkaloids 3.7.3. Sesquiterpene Alkaloids 3.7.4. Diterpene Alkaloids 3.7.5. Sesterterpene and Triterpene Alkaloids 3.7.6. Steroidal Alkaloids 4. Summary

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Stereocontrolled Formation of Three Contiguous Stereogenic Centers by Free Radical Cyclization – Synthesis of (+)‐Iridomyrmecin and (–)‐Iso‐iridomyrmecin – Formal Synthesis of δ‐Skythantine

Cited by 13 publications

References 32 publications

Stereoselective Chemical Defense in the Drosophila Parasitoid Leptopilina heterotoma is Mediated by (−)-Iridomyrmecin and (+)-Isoiridomyrmecin

Stereoselective Chemical Defense in the Drosophila Parasitoid Leptopilina heterotoma is Mediated by (−)-Iridomyrmecin and (+)-Isoiridomyrmecin

Divergent Diastereoselective Synthesis of Iridomyrmecin, Isoiridomyrmecin, Teucrimulactone, and Dolicholactone from Citronellol

Alkaloids

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