RESUMO
An enantioselective total synthesis of the natural amino acid (2S,4R,5R)-4,5-di-hydroxy-pipecolic acid starting from D-glucoheptono-1, 4-lactone is presented. The best sequence employed as a key step the intramolecular nucleophilic displacement by an amino function of a 6-O-p-toluene-sulphonyl derivative of a methyl D-arabino-hexonate and involved only 12 steps with an overall yield of 19%. The structures of the compounds synthesized were elucidated on the basis of comprehensive spectroscopic (NMR and MS) and computational analysis.
Assuntos
Aminoácidos Cíclicos/química , Aminoácidos Cíclicos/síntese química , Química Orgânica/métodos , Ácidos Pipecólicos/química , Azidas/química , Catálise , Modelos Moleculares , Piperidinas/síntese química , Piperidinas/química , Teoria Quântica , TermodinâmicaRESUMO
Nigriventrine was isolated from the "armed" spider Phoneutria nigriventer, in which it constitutes about 0.4% of the total venom content. Its structure was determined to be [1,1'-(1-hydroxyhydrazine-1,2-diyl)bis(oxy)bis(4-hydroxy-2,6-dioxopiperidine-4 carboxylic acid)] by NMR, HR-ES/IMS and MS/MS methods. The intracerebroventricular application of nigriventrine in rat brain, followed by the detection of c-Fos protein expression, indicated that the compound was neuroactive in the motor cortex, sensory cortex, piriform cortex, median preoptic nucleus, dorsal endopiriform nucleus, lateral septal nucleus and hippocampus of rat brain. Nigriventrine causes convulsions in rats, even when peripherally applied.