Stereoselektivna fotokemijska dearomatizacija elektronima bogatih arena

master's thesis

• Title (english): Stereoselective photochemical dearomatization of electron-rich arenes
• Author: Karlo Petrić
• Mentor: Nikola Topolovčan (mentor)
• Committee member: Đani Škalamera (predsjednik povjerenstva)
• Committee member: Iva Juranović Cindrić (član povjerenstva)
• Committee member: Dominik Cinčić (član povjerenstva)
• Committee member: Vesna Petrović Peroković (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2022-09-30, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U sklopu ovog diplomskog rada istraženo je fotokemijsko dearomativno ciklopropaniranje
elektronima bogatih arena. Reakcije dearomatizacije derivata benzena omogućuju dizajn
sintetskog puta koji uključuje pretvorbu povoljnih i lako dostupnih aromatskih π-sustava u
strukturno kompleksne molekule u samo nekoliko konvergentnih sintetskih koraka. Kao
supstrat ciklopropaniranja korišten je 1,2-dimetoksibenzen. Njegovim je ciklopropaniranjem
karbenima generiranim in situ iz arildiazoestera pod plavom svjetlosti dobiven niz meso
norkaradiena koji su desimetrizirani ponovnim fotokemijskim ciklopropaniranjem. Sintetski
potencijal dobivenih produkata je potvrđen [4+2] cikloadicijom in situ generiranog benzina na
norkaradien, kao i reakcijom σ-bishomobenzena s BBr3 čime je postignuto otvaranje jednog
ciklopropanskog prstena i stvaranja α-metoksiketona koji je u isto vrijeme i Michealov
akceptor, što omogućuje daljnje transformacije. Pripravljeni polazni spojevi, kao i konačni
produkti, okarakterizirani su analitičkim tehnikama poput nuklearne magnetne rezonancije,
spektroskopijom masa i difrakcijom rentgnenskog zračenja na monokristalu.

Abstract (english)

Focus of this diploma thesis is photochemical dearomative cyclopropanation of electron-rich
arenes. Dearomatizations of benzene derivatives allows design of synthetic pathway, which
includes transformation of cheap and readily avalilable aromatic π-systems into structurally
complex molecules in several convergent synthetic steps. 1,2-dimethoxybenzene was used as a
substrate for the cyclopropanation. Cyclopropanation of 1,2-dimethoxybenzene via carbene
transfer of photochemically in situ generated carbenes from aryldiazoesters under blue light
resulted with a number of meso norcaradiens. Resulting meso norcaradiens were subjected to
desymmetrizations via secondary photochemical cyclopropanation. Transformation potential
of produced norcaradiens and σ-bishomobenzenes has been confirmed by [4+2] cycloadition of
in situ generated benzyne onto norcaradiene, as well as by a reaction of σ-bishomobenzene with
BBr3 that caused cyclopropane ring opening resulting in an α-methoxyketone that is also a
Michael acceptor allowing further transformations. Prepared starting materials, as well as
resulting compunds were characterized by analytical techniques such as nuclear magnetic
resonance spectroscopy, mass spectrometry and x-ray diffraction on a monocrystal.

• Keywords: ciklopropaniranje; dearomatizacija; fotokemija; karbeni; norkaradieni
• Keywords (english): cyclopropanation; dearomatization; photochemistry; carbenes; norcaradienes
• Language: croatian
• URN:NBN: urn:nbn:hr:217:978973
• 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: 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: 2023-03-30
• Created on: 2022-10-24 14:28:47