Sinteza prekursora marinoazepinona

master's thesis

• Title (english): Synthesis of the marinoazepinone precursor
• Author: Filip Novković
• Mentor: Irena Dokli (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Iva Juranović Cindrić (član povjerenstva)
• Committee member: Željka Soldin (član povjerenstva)
• Committee member: Vesna Petrović Peroković (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 diplomskom radu istraživan je postupak totalne sinteze marinoazepinona A i B te sinteza
njihovih prekursora. U prvom koraku, pirolski dušik je zaštićen, a zatim regioselektivno
bromiran na C–3 položaju. Bromirani zaštićeni pirol preveden je reakcijom Miyaurine
borilacije u boronat. U sljedećem koraku ispitani su uvjeti za Suzuki–Miyaura reakciju
dobivenog boronata s 2–jodanilinom pri čemu je pripravljen adukt zaštićenog pirola i 2–
jodanilina. Nakon deprotekcije zaštitne skupine pirola, provedeno je selektivno bromiranje na
C–2 položaju pirola, te su na bromiranom aduktu sva tri slobodna dušika ponovno zaštićena.
Dobiveni bromid korišten je za istraživanje reakcije transmetalacije korištenjem n–butillitija
ili izo–propilmagnezijevog klorida te adicije na prikladne spojeve s ciljem dobivanja produkta
s karbonilnom skupinom kao prekusora za daljnju ciklizaciju. Marinoazepinoni A i B kao
ciljni spojevi nisu uspješno sintetizirani, no pripravljeni su vrijedni prekursori koji će poslužiti
u daljnjem istraživanju njihove totalne sinteze.

Abstract (english)

This thesis describes research of total synthesis of marinoazepinones A and B as well as the
synthesis of their precursors. In the first step, the pyrrole nitrogen is protected and then
regioselectively brominated at the C–3 position. The brominated protected pyrrole was
converted by Miyaura borylation reaction into boronate. In the next step, the conditions for
the Suzuki–Miyaura reaction of the obtained boronate with 2–iodoaniline were studied to
prepare an adduct of protected pyrrole and 2–iodoaniline. After deprotecting the pyrrole ring
of the adduct, selective bromination was performed at the C–2 position of the pyrrole ring,
and all three free nitrogens on the brominated adduct were protected. Obtained bromide was
used to investigate transmethalation using n–butyllithium or isopropylmagnesium chloride
and for the addition to the suitable compounds in order to obtain a ketone product as a
precursor for further cyclization. Marinoazepinones A and B as target compounds have not
been synthesized, but valuable precursors have been prepared which will contribute to further
research of their total synthesis.

• Keywords: bromiranje; boronični ester; pirol; retrosinteza; Suzuki–Miyaura reakcija; totalna sinteza
• Keywords (english): bromination; boronic ester; pyrrole; retrosynthesis; Suzuki–Miyaura reaction; total synthesis
• Language: croatian
• URN:NBN: urn:nbn:hr:217:312985
• 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
• Created on: 2021-03-17 12:22:43