ABSTRACT
Social insect societies are characterized by division of labour and communication within the colony. The most frequent mode of communication is by chemical signals. In general, pheromones elicit specific responses in the receiver, although reactions may vary depending on the receiving individual's physiological or motivational state. For example, it has been shown that pheromones can elicit different responses in morphological worker castes. However, comparably little is known about such effects in worker castes of monomorphic species. Here, we comprehensively studied a monomorphic species showing age polyethism, the thelytokous ant Platythyrea punctata Our analyses revealed that the species' alarm pheromone consists of (S)-(-)-citronellal and (S)-(-)-actinidine, and is produced in the mandibular glands. Ants responded with increased movement activity and increasing ant density towards the pheromone source in whole-colony bioassays, confirming the alarming effect of these compounds. We found age classes to differ in their absolute pheromone content, in the propensity to release alarm pheromone upon disturbance and in their reaction towards the pheromone. Absolute amounts of pheromone content may differ simply because the biosynthesis of the pheromone begins only after adult eclosion. Nonetheless, our results indicate that this clonal species exhibits age-related polyethism in the emission of as well as in the response to its alarm pheromone.
Subject(s)
Ants , Animals , Behavior, Animal , Biological Assay , PheromonesABSTRACT
Detecting danger is one of the foremost tasks for a neural system. Larval parasitoids constitute clear danger to Drosophila, as up to 80% of fly larvae become parasitized in nature. We show that Drosophila melanogaster larvae and adults avoid sites smelling of the main parasitoid enemies, Leptopilina wasps. This avoidance is mediated via a highly specific olfactory sensory neuron (OSN) type. While the larval OSN expresses the olfactory receptor Or49a and is tuned to the Leptopilina odor iridomyrmecin, the adult expresses both Or49a and Or85f and in addition detects the wasp odors actinidine and nepetalactol. The information is transferred via projection neurons to a specific part of the lateral horn known to be involved in mediating avoidance. Drosophila has thus developed a dedicated circuit to detect a life-threatening enemy based on the smell of its semiochemicals. Such an enemy-detecting olfactory circuit has earlier only been characterized in mice and nematodes.
Subject(s)
Drosophila Proteins/agonists , Drosophila melanogaster/drug effects , Nerve Tissue Proteins/agonists , Olfactory Bulb/drug effects , Receptors, Odorant/agonists , Sensory Receptor Cells/drug effects , Wasps/metabolism , Alkaloids/pharmacology , Animals , Animals, Genetically Modified , Behavior, Animal/drug effects , Bridged Bicyclo Compounds, Heterocyclic/pharmacology , Drosophila Proteins/genetics , Drosophila Proteins/metabolism , Drosophila melanogaster/genetics , Drosophila melanogaster/parasitology , Drosophila melanogaster/physiology , Female , Iridoids/pharmacology , Larva/drug effects , Larva/genetics , Larva/parasitology , Larva/physiology , Mutant Proteins/agonists , Mutant Proteins/metabolism , Nerve Tissue Proteins/genetics , Nerve Tissue Proteins/metabolism , Odorants , Olfactory Bulb/metabolism , Oviposition , Protein Isoforms/agonists , Protein Isoforms/metabolism , Pyridines/pharmacology , Receptors, Odorant/genetics , Receptors, Odorant/metabolism , Sensory Receptor Cells/metabolism , Signal Transduction , Terpenes/pharmacologyABSTRACT
The iridoid natural products iridomyrmecin, isoiridomyrmecin, teucriumlactone, and dolicholactone were prepared from citronellol using a divergent diastereoselective approach. Key steps include a highly diastereoselective enamine/enal cycloaddition and the selective reduction of masked aldehyde functionalities by ionic hydrogenation.
Subject(s)
Iridoids/chemical synthesis , Monoterpenes/chemistry , Acyclic Monoterpenes , Iridoids/chemistry , Molecular Conformation , StereoisomerismABSTRACT
The ant-associated iridoids nepetalactol, actinidine, dolichodial, isoiridomyrmecin, and dihydronepetalactone were prepared from citronellal using a divergent approach. Key features include a three-step synthesis of the individual antipodes of actinidine by a novel tandem cycloaddition/pyridine formation and a facile diastereoselective synthesis of both enantiomers of dolichodial.
Subject(s)
Iridoids/chemical synthesis , Iridoids/chemistry , Molecular Conformation , StereoisomerismABSTRACT
Several different approaches to the A-ring functionalization of an advanced, highly functionalized diosphenol precursor to Taxol are described. The first phase of the undertaking consists of an assessment of those reagents conducive to reaction at the enolic oxygen (silylation, methylation, allylation, and acylation). Transformations involving an alternative attack at the enol carbon center (bromination, selenation) have also been defined. Sodium borohydride reduction operates from the beta-face of C-14 as long as the C-1 hydroxyl is not protected so as to offer steric exclusion. Complications associated with various aspects of these methodological undertakings are addressed. The most advanced oxygenation achievements were realized by way of a noteworthy sequence involving epoxidation of the O-methyl ether, methanolysis under mildly acidic conditions, and regioselective oxidation of diol 38 to give 39.
Subject(s)
Paclitaxel , Phenols/chemistry , Prodrugs , Molecular Structure , Paclitaxel/chemical synthesis , Paclitaxel/chemistry , Prodrugs/chemical synthesis , Prodrugs/chemistry , StereoisomerismABSTRACT
The stereochemical course of the epoxidation of the silyl enol ethers of 2-tert-butyldimethylsilyloxycycloheptanone and -cyclooctanone has been investigated and shown to proceed exclusively anti to the existing alpha-substituent. 2-(Benzyloxy)cyclooctanone behaves similarly, and the presence of a transannular double bond does not alter the outcome. Alpha-ketol rearrangements are seen to operate during ensuing fluoride ion-induced removal of the silyl protecting groups in select examples. The preferred means for generating the cis isomers of the alpha,alpha'-dihydroxy cycloalkanones involves methylenation of the monoprotected trans-dihydroxy ketones with the Nysted reagent, followed by oxidation and subsequent reduction with sodium borohydride. Ozonolysis and fluoride ion-induced desilylation complete the route.
ABSTRACT
[reaction: see text] Apha,alpha'-dihydroxy ketones having two OH groups that can come into close proximity react with phosgene in the presence of DMAP to produce 1,3-dioxane-2,5-diones. When covalent bonding in this manner is prohibited, alternate reaction pathways can in principle be adopted. Of these, the generation of spiro epoxy carbonates is shown to be feasible in three examples. In other cases, the alpha-ketol rearrangement precedes diacylation.
ABSTRACT
The convergent, stereocontrolled synthesis of enantiopure stereoisomeric 9,10-cyclic acetals, whose designed role was to serve as potential precursors to Taxol, is reported. These advanced intermediates are multiply functionalized and carry a bridgehead alpha-ketol array which was key to isomerization into the proper framework. In agreement with relative strain energy values obtained by MM3 calculations, a dichotomy was observed between these two families. While the trans-fused acetals failed to undergo bridge migration, their cis counterparts did so efficiently. In fact, isomerization was sufficiently rapid that oxygenation at C2 was now precluded. The operation of several unusual transannular hydride shifts is also detailed.
Subject(s)
Acetals/chemistry , Ketones/chemistry , Paclitaxel/chemistry , Paclitaxel/chemical synthesis , Catalysis , Combinatorial Chemistry Techniques , Cyclization , Indicators and Reagents , Molecular Structure , Neuraminidase , Oxidation-Reduction , StereoisomerismABSTRACT
The feasibility of the title reaction has been pursued for the purpose of advancing a concise total synthesis of Taxol. Of the two closely related series examined, the first featured an exo-methylene group at C4. The second consisted of an alpha-epoxide at that site. Strikingly, the olefinic construct proved inert to attempted alpha-ketol rearrangement. In contrast, the oxiranyl derivative isomerized smoothly. The reaction sequence associated with arrival at taxane 18 is short (15 steps from a D-camphor derivative) and notably efficient. The thermodynamic issues that are raised by this investigation have been clarified by an assessment of molecular mechanics-derived (MM3) steric energy calculations.
Subject(s)
Bridged-Ring Compounds/chemistry , Bridged-Ring Compounds/chemical synthesis , Paclitaxel/chemistry , Taxoids , Catalysis , Combinatorial Chemistry Techniques , Crystallography, X-Ray , Cyclization , Hydroxylation , Indicators and Reagents , Molecular Structure , Oxidation-Reduction , Stereoisomerism , Structure-Activity Relationship , ThermodynamicsABSTRACT
An unprecedented high barrier to ring inversion [Eq. (1)] prevents 1 from engaging in bifacial complexation with lithium ions. The X-ray crystal structure analysis of this hexaspiro compound corroborates the adoption of a cyclohexane chair with all six C-O bonds projected equatorially (1-eq).
