Priprava policikličkih manokonjugata i njihovo kompleksiranje s β-ciklodekstrinom

master's thesis

• Title (english): Synthesis of polycyclic mannoconjugates and complexation with β-cyclodextrin
• Author: Doroteja Radonić
• Mentor: Vesna Petrović Peroković (mentor)
• Committee member: Vesna Petrović Peroković (predsjednik povjerenstva)
• Committee member: Iva Juranović Cindrić (član povjerenstva)
• Committee member: Željka Soldin (član povjerenstva)
• Committee member: Ines Primožič (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2021-02-19, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U ovom diplomskom radu opisan je postupak sinteze tri policiklička manokonjugata, estera 2-
(α-D-manopiranoziloksi)octene kiseline (exo-norbornan-2-il (14), naftalen-2-il (15) i 5,6,7,8-
tetrahidronaftalen-1-il (16)) te priprava prekursora 12 za sintezu analognog antracen-2-ilnog
estera. Zaštićeni manokonjugati 9-12 dobiveni su reakcijom tetrabenziliranog manoznog
prekursora sa slobodnom anomernom hidroksilnom skupinom i odgovarajućeg policikličkog
estera bromoctene kiseline u uvjetima Williamsonove sinteze etera. Esteri bromoctene
kiseline 3-6 dobiveni su reakcijom odabranog policikličkog alkohola i bromacetil-bromida. Za
dobivanje konačnih produkata 14-16 benzilna zaštita s manokonjugata 9-11 uklonjena je
reakcijom katalitičke hidrogenolize. Prilikom debenziliranja naftalen-1-il-2-(2,3,4,6-tetra-Obenzil-
α-D-manopiranoziloksi)acetata (10), umjesto očekivanog manokonjugata dobiven je
spoj 16. Strukture svih sintetiziranih spojeva potvrđene su NMR spektroskopijom (1H i 13C), a
neke od njih i spektrometrijom masa (MS). Policiklički manokonjugati sintetizirani su u svrhu
daljnjeg ispitivanja njihovog kompleksiranja s β-ciklodekstrinom, a nastajanje inkluzijskih
kompleksa u vodi preliminarno je potvrđeno 2D NMR spektroskopijom (1H-1H ROESY).

Abstract (english)

This diploma thesis describes the syntheses of three polycyclic esters of 2-(α-Dmannopyranosyloxy)
acetic acid (exo-norbornane-2-yl (14), naphthalene-2-yl (15) and 5,6,7,8-
tetrahydronaphthalene-1-yl (16)) and the preparation of the precursor 12 for the syntheses of the
analogous anthracene-2-yl ester. The protected mannoconjugates 9-12 were prepared by the
reaction of the tetrabenzylated mannose precursor with the free anomeric hydroxyl group and the
corresponding polycyclic ester of a bromoacetic acid in the conditions of Williamson ether
synthesis. The esters of the bromoacetic acid 3-6 were prepared by the reaction of the selected
polycyclic alcohol and a bromoacetyl bromide. The final products 14-16 were obtained by
removing the benzyl protection from mannoconjugates 9-11 by means of catalytic hydrogenolysis.
During the debenzylation of naphthalene-1-yl-2-(2,3,4,6-tetra-O-benzyl-α-Dmannopyranosyloxy)
acetate (10), instead of the expected mannoconjugate, compound 16 was
obtained. The structures of all synthesized compounds were confirmed by 1H and 13C NMR
spectroscopy and/or by mass spectrometry. Polycyclic mannoconjugates were synthesized for the
purpose of further investigating their complexation with β-cyclodextrin and the formation of
inclusion complexes in water was preliminarily confirmed by 2D NMR spectroscopy (1H-1H
ROESY).

• Keywords: β-ciklodekstrin; katalitičko hidrogeniranje; policiklički manokonjugati; zaštitne skupine
• Keywords (english): catalytic hydrogenation; β-cyclodextrin; polycyclic mannoconjugates; protection groups
• Language: croatian
• URN:NBN: urn:nbn:hr:217:072309
• Project: Number: IP-2019-04-9560; Title: Koordinacijske reakcije makrocikličkih liganada u otopini; Title: Coordination Reactions of Macrocyclic Ligands in Solution; Acronym: MacroSol; Leader: Vladislav Tomišić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2023-02-19
• Created on: 2021-03-09 13:05:47