Priprava višesupstituiranih ciklopentadiena cirkonocenom potpomognutom ciklizacijom dienina

master's thesis

• Title (english): Synthesis of multisusbstituted cyclopentadienes by zirconocene-mediated cyclization of dienynes
• Author: Marko Gobin
• Mentor: Nikola Topolovčan (mentor)
• Committee member: Đani Škalamera (predsjednik povjerenstva)
• Committee member: Aleksandra Maršavelski (član povjerenstva)
• Committee member: Iva Juranović Cindrić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2023-11-22, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U okviru ovog diplomskog rada razvijena je metodologija priprave višesupstituiranih
ciklopentadiena u nekoliko konvergentnih sintetskih koraka pri čemu postoji mogućnost
selektivnog uvođenja i variranja veličine pojedinih supstituenata na ciklopentadienskom
prstenu. Sintetski put započinje regioselektivnom bromalilacijom disupstituiranih alkina pri
čemu nastaju odgovarajući bromdieni s reaktivnom ugljik-halogen vezom. To je ključno za
provedbu Sonogashirine reakcije s terminalnim acetilenima kako bi se generirali nekonjugirani
dienini. Ciklizacijom dienina pomoću niskovalentnog organocirkonija (Negishijev reagens)
pripravljeni su ciklopentadieni s exo-cikličkom dvostrukom. U posljednjem koraku, kiselinom
kataliziranom exo-to-endo izomerizacijom exo-cikličke dvostruke veze ciklopentadiena
pripravljeni su tetrasupstituirani ciklopentadieni. Strukture pripravljenih spojeva potvrđene su
analitičkim tehnikama i postupcima (NMR, MS).

Abstract (english)

The methodology for the preparation of multisubstituted cyclopentadienes in several
convergent synthesis steps was developed within this master's thesis. This allows for the
selective introduction and varation of the size of individual substituents on the cyclopentadienyl
ring. The synthetic route starts with the regioselective bromallylation of disubstituted alkynes,
yielding the corresponding bromodienes with a reactive carbon-halogen bond, which is crucial
for carrying out the Sonogashira reaction with terminal acetylenes to generate non-conjugated
dienynes. By cyclizing the dienyne using low-valent zirconium compounds (Negishi reagent),
cyclopentadienes with an exo-cyclic double bond were prepared. In final step, through acid
catalyzed exo-to-endo isomerisation of the exo-cyclic double bond of the cyclopentadiene,
tetrasubstituted cyclopentadienes were prepared. The structures of the prepared compounds
were confirmed using analytical techniques and procedures such as (NMR, MS).

• Keywords: cirkonocenom potpomognuta ciklizacija; Negishijev reagens; nekonjugirani dienini; regioselektivna bromalilacija; višesupstituirani ciklopentadieni
• Keywords (english): multisubstituted cyclopentadienes; Negishi reagent; non-conjugated dienynes; regioselective bromallylation; zirconocene-mediated cyclization
• Language: croatian
• URN:NBN: urn:nbn:hr:217:118344
• Project: Number: IP-2018-01-4053; Title: Nove strategije za pripravu tetrasupstituiranih kiralnih centara: asimetrične katalitičke reakcije usmjerene protuanionom; Acronym: NSYNC-ACDC; Leader: Matija Gredičak; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Graduate university studies in chemistry; specializations in: Graduate university studies in chemistry; Course: Graduate university studies in chemistry; Study programme type: university; Study level: graduate; Academic / professional title: sveučilišni/a magistar/magistra kemije (sveučilišni/a magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Embargoed access; Embargo expiration date: 2024-05-22
• Created on: 2023-11-27 11:53:05