BICYCLICAL COMPOUNDS CHEMISTRY

Author: MELÉNDEZ SERRANO JAISIEL.
Year: 2005.
University: ALICANTE.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The report describes the implementation of several sintones metilidénicos dianiónicos the synthesis of cyclic ethers through intermediate organolíticos. The break-lowering links carbono-heteroátomo present in these sintones using lithium metal and an amount in excess of catalytic areno 4.4 '-di-terc-butilbifenilo in the presence of compounds carbonílicos or epoxides, has enabled obtaining metilidendioles. These have been transformed into different cyclic ethers through conventional reactions such as hidroboración-oxidación, yodoeterificación and ozonólisis. All structures oxygen prepared belonging to families of compounds that are widely distributed in nature and that, like some of synthetic origin, have biological activity destacada.En Chapter I detailing the implementation of 2,3-dicloroprop-1- eno as sintón 2,3-dianiónico of propene and use in the preparation of 1, 5-dioxaespiro [2.4] heptanos. In addition, it includes the ability to use these systems espiránicos as precursors supplies lactones 1,5-dioxaespiro [2.4] heptan-4-onas. In Chapter II contains implementing 2-clorometil-3- (2-metoxietoxi) prop-1-eno as sintón dianiónico of trimetilenmetano and their use in the synthesis of perhidrofuro [2,3-b] piranos and 1.7 - dioxaespiro [4.4] nonanos. It also describes the usefulness of the latter as precursors suitable lactones 1,7-dioxaespiro [4.4] nonan-6-onas.Por Finally, in Chapter III examines the desirability of 4-fenilsulfanil-2- (2 - fenilsulfaniletil) but-1-eno as new sintón 1,5-dianiónico of 3-metilidenpentano and their use in the synthesis of cis-perhidropirano [2,3-b] piranos, 1,7-dioxaespiro [4.5] deans and 1, 6-dioxaespiro [4.4] nonanos. This chapter also deals with the preparation of trans-perhidropirano [2,3-b] piranos by isomerization of cis-isomers concerned, as well as oxidation system 1, 7-dioxaespiro [4.5] dean to 1,7-dioxaespiro [4.5] decan-6-ona.

Author: MAIRAL LERGA TERESA.
Year: 2005.
University: BARCELONA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS Y AMBIENTALES DE BARCELONA (CSIC).

Summary: The neurodegenerative diseases have as a common denominator the deposition of amyloid fibers in some vital organs and brain. One of the amyloid diseases that stands out for being a good model for this type of peripheral neuropathies are diseases caused by the plasma protein transport transtiretina (TTR). One of the functions of TTR is the transport of horonas thyroid (T4). TTR sedisocia in monomers prior to the formation of amyloid fibers. Thus, a strategy to stabilize the tetrámero through miméticos natural substrate (hormone thyroxine) opens the opportunity to advance amyloid diseases associated with TTR. Since 1998 the group JW Kelly of the Department of Chemistry Scripps Reserach Institute (California, USA) has been working on a new strategy for the amyloidosis of the transtiretina. This strategy is based on the stabilization of tetrámero by binding ligands -moléculas small that mimeticen union to thyroxine but who do not have hormonal activity or mimetic of thyroxine. Among other highlights the inhibitory potency of non-steroidal anti - (NSAIDs) such as dflunisal or acid flufenámico. Thus, based on the idea that the natural ligands of the transtiretina contain atoms of iodine in its structure, it was decided to iodize diflunisal and acid flufenámico and analyze their biological activity. The result was that the yododiflunisal was more active than their non-iodized similar but not the same effect occurred with acid flufenámico. Therefore, according to this line, one of the main objectives of this thesis is the synthesis and characterization of 20 derivatives diflunisal, 16 of which have not been described previously in the literature and show that the addition of iodine atoms through agent iodization IPy2BF4, the ability inhibitory potency of these derivatives. Small variations produced in diflunisal are made on the ring salicylic, leaving 2.4 difluorofenilo unchanged. A second objective of this thesis has been deepening in various stages of the process amiloidogénico. Thus, through techniques espectrospía UV-Fy circular dichroism has analyzed the stability of TTR native and one of its variants Y78F in the presence of inhibitors diflunisal and yododiflunisal. Moreover, the fibers formed by peptides amilodogénicos, have been analyzed by Congo Red staining and by optical microscopy, taking as a model fibers formed by TTR native TTRY78F and insulin. The latter have also been marked by espectroscipía UV qualitatively.

Author: DÍAZ MORILLO CRISTINA.
Year: 2005.
University: NACIONAL DE EDUCACIÓN A DISTANCIA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: Given the importance of presenting derivatives enantiopuros of camphor and fencona in stereoselective synthesis, in this thesis has been prepared estereocontroladamente, from these ketones bicíclicas natural derivatives bridgehead funcionalizados also in other positions of the ring norbornánico and the development of correlation studies estructura-reactividad related to: 1 - Activity certain ligands type amino alcohol in asymmetric catalysis. B-Reactivity, stability and structure cations 1-norbornilo. It has carried out the transformation estereocontrolada of 2-metilennorbornanos C1-sustituidos derived from camphor and fencona in the corresponding espiro [norbornano-2, 2'-oxiranos] C1-sustituidos. Subsequently, it has studied the reactivity of the same nucleotide opposite of a different nature in order to explore the evolution of the corresponding norbornanolatos. In addition, there has been an interesting correlation study estructura-reactividad in cations 1-norbornilo, generated by solvolisis Ethanol aqueous of the corresponding triflatos of esprio [norbornano-2-2'-oxiran] -1-ilo. Furthermore, we have synthesized new derivatives C10-sustituidos of camphor and fencona from 10-trifliloxialcanfor and 10-trifliloxifencona, including the C10-N-sustituidos, using a simple and highly enantioespecífico. These triflatos primary type neopentílico, synthesized for the first time, have proved to be excellent reagents alkylation electrófila. Based on the methodology has brought to our point working group to obtain derivatives C10-sustituidos of camphor, has developed a new route which is a simple method, innovative and highly efficient for the preparation of derivatives enantiopuros C9 C10-disustituidos the camphor, avoiding the problems encountered in the classical route for obtaining them from 9,10-dibromoalcanfor. The gamma-amino alcohols nature norbornánica synthesized were tested as ligands in the catalyzed asymmetric addition of dietilzinc to benzaldehyde. The results have enabled us to expand the study begun in our research group on the influence of the structure of the ligand on the catalytic role of the same. In addition, it has carried out a comparative study with respect to beta-amino alcohols and *- similar synthesized and tested previously commented on the reaction skewed by our working group.

Author: Peransí Llopis Sergio Manuel.
Year: 2006.
University: VALENCIA.
Place of defense: Facultad de Química.
Place of preparation: Facultad de Química.

Summary: Different receivers have been designed for the study and appreciation of species cationic, anionic, and neutral amino acids zwitteriónicos. Through various experiments using techniques UV fluorescence and NMR.