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A Stimac

Publications and source records attributed to A Stimac.

6 recordsLinked to original sources
PubMed2000

Stereoselective synthesis of 1,2-cis- and 2-deoxyglycofuranosyl azides from glycosyl halides.

Protected 1,2-cis glycofuranosyl azides with alpha-D-ribo, beta-D-arabino and 2-deoxy-2-fluoro-beta-D-arabino configurations were efficiently prepared from the appropriate 1,2-trans glycosyl halides bearing non-participating 0-2 substituent by inversion with sodium azide under phase transfer catalytic conditions (80-85% yields, 90-96% de). The same method failed to result in sufficiently good beta-selectivity starting from 2-deoxy-3,5-di-O-(p-toluoyl)-alpha-D-ery-thro-pentofuranosyl chloride (5alpha) (40% de). The selectivity in favour of the protected 2-deoxy-beta-D-erythro-pentofura-nosyl azides was greatly improved (74-80% de) by treating 5alpha and its p-chlorobenzoyl analog 6alpha with cesium or potassium azide in dimethylsulfoxide at room temperature (83-85% yields).

Azides↗
PubMed2000

Studies on the origin of stereoselectivity in the synthesis of 1,2-trans glycofuranosyl azides.

The stereoselectivity of the 1,2-trans directed, Lewis acid-catalysed azidation of peracylated furanoses was found to depend on the reactivity of the azide donor (azide nucleophilicity) and the configuration at the anomeric centre relative to the neighbouring 2-O-acyl group. Reactions of 1,2-trans glycosyl esters with highly nucleophilic azide donors, generated from SnCl4 and Me3SiN3, were stereospecific. The results are interpreted in terms of the rapid reaction of the azide species with bicyclic 1,2-acyloxonium (1,2-O-alkyliumdiyl-D-glycofuranose) ions, which were the primarily formed reactive intermediates. When using 1,2-cis glycosyl esters as starting materials the selectivity was reduced (90-94% de); the same is true with 1,2-trans counterparts if less nucleophilic Me3SiN3 in combination with Me3SiOTf catalyst was used. This occurred due to the appearance of the more reactive but less selective oxocarbenium (glycofuranoxonium) ions either as primarily formed reactive intermediates in the former case or after equilibration with acyloxonium ions in the latter case. Protected 1,2-trans beta-D-glycofuranosyl azides with ribo, xylo and 3-deoxy-erythro-pento configurations were best prepared from the corresponding glycosyl esters using 0.05 equivalents of SnCl4, i.e., under anomerization-free conditions. Azidation of methyl glycofuranosides proceeds with inferior (80-90% de) and less predictable selectivity irrespective of the starting anomeric configuration.

Azides↗
PubMed2000

Endoscopic third ventriculostomy with ultrasonic contact microprobe.

The authors describe their first clinical experiences in endoscopic third ventriculostomy (ETV) with the original ultrasonic contact microprobe (UCM) designed at the Department of Neurosurgery in Zagreb. The analysis includes the clinical course of disease in eight patients submitted to surgery from May to September 1999 (3 men and 5 women, from 14 to 61 years of age). Surgery was performed in patients with neurological symptoms of elevated intracranial pressure and neuroradiological evidence of non-communicating hydrocephalus caused by mesencephalic aqueduct stenosis. The perforation in the base of the third brain ventricle made by the ultrasonic contact microprobe was widened by a balloon catheter. The authors have come to conclusion that the ETV when performed by contact ultrasonic microprobe is a small risk procedure in case of non-communicating hydrocephalus. For its small diameter (1.6 mm) and simple handling the newly designed contact ultrasonic microprobe is very suitable for use in neuroendoscopy as it enables fenestration of the third brain ventricle with minimal thermal and ultrastructural damage to the adjacent neurovascular structures. Further research will be focused on defining indications for the use of the device in other neuroendoscopic procedures as well.

Adolescent↗
PubMed2000

Ultrasonic contact microprobe: experimental results.

At the Department of Neurosurgery, School of Medicine, University of Zagreb, the original ultrasonic contact microprobe (UCM) was designed. The efficacy of the instrument was tested on 120 brains of Wistar strain rats. The authors have been investigating the possibility of transferring high-energy ultrasound through the titanium wire probe of the device and the efficacy of UCM in controlled punctiform destruction of brain tissue. Light and electron microscope assessed the lesions made in the brains of experimental rats. Histological findings in the preparations showed the zone of thermal injuries from 100 to 200 microm and the zone of ultrastructural changes from 200 to 300 microm, indicating the sparing effect of the microprobe with regard to the adjacent neurovascular structures. The small dimensions of the ultrasonic contact microprobe (1.6 mm) enable its introduction through the operating canal of a ventriculoscope. Further research is expected to show the efficacy of the ultrasonic contact microprobe in endoscopic neurosurgery.

Animals↗
PubMed2000

Methyl 1-

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Journal Article↗