20.500.12556/DKUM-85857 Light-induced palladium-catalyzed Buchwald Hartwig amination master's thesis Svetlobno inducirana s paladijem katalizirana Buchwald-Hartwig aminacija The goal of this master’s thesis was to investigate the use of light to enable the acceleration of the Buchwald-Hartwig amination of deactivated aryl chlorides with an ammonium source using a newly developed and optimized state-of-the-art catalyst system. A photoreactor was designed, modelled, and constructed to allow for a reproducible reaction setup under controlled conditions. The optimal light source and reaction conditions were investigated using a model reaction. Conversion of the starting material, product yield and potential byproducts were quantified by gas chromatography (GC) analysis and confirmed by mass spectroscopy (GC/MS). The use of light (3 W 447 nm) enabled the accelerated conversion of aryl chlorides towards the amination products even at room temperature in 2 hours, which is a remarkable improvement upon the previously reported state-of-the-art. Under optimized conditions, the highest yield (88 %) was achieved using a catalyst complex formed from β-methyl naphthyl (β-MeNAP) palladium bromide and the sterically demanding ligand AdBrettPhos. The structure of the complex crystal was elucidated using X-ray crystallography after the crystallization of the catalyst species. Cilj tega magistrskega dela je bil raziskati uporabo svetlobe za pospešitev Buchwald-Hartwigove aminizacije deaktiviranih arilkloridov z amonijevim virom z uporabo novo razvitega in optimiziranega sodobnega katalizatorskega sistema. Fotoreaktor je bil zasnovan, modeliran in izdelan, da bi omogočil ponovljivo postavitev reakcije v nadzorovanih pogojih. Optimalni vir svetlobe in reakcijski pogoji so bili raziskani z uporabo modelne reakcije. Pretvorba izhodne snovi, izkoristek produkta in morebitni stranski produkti so bili količinsko opredeljeni z analizo s plinsko kromatografijo (GC) in potrjeni z masno spektroskopijo (GC/MS). Uporaba svetlobe (3 W 447 nm) je omogočila pospešeno pretvorbo arilkloridov v produkte aminizacije tudi pri sobni temperaturi v dveh urah, kar je izjemen napredek glede na predhodno opisano stanje. Pri optimiziranih pogojih je bil največji izkoristek (88 %) dosežen z uporabo katalizatorskega kompleksa, tvorjenega iz β-metilnaftil paladijevega bromida (β-MeNAP) in sterično zahtevnega liganda AdBrettPhos. Po kristalizaciji katalizatorske vrste je bila z rentgensko kristalografijo pojasnjena struktura kompleksnega kristala. Buchwald-Hartwig amination photochemistry palladium room temperature ammonium salt Buchwald-Hartwig aminacija fotokemija paladij sobna temperatura amonijeva sol true true false [A. Oštir] Angleški jezik Slovenski jezik Magistrsko delo/naloga 2023-09-15 02:27:13 2023-10-03 12:44:44 2023-11-08 03:09:42 0000-00-00 00:00:00 2023 0 Maribor 0 Bochum 1 spletni vir (1 datoteka PDF (XII, 45 f.)) 0000-00-00 NiDoloceno NiDoloceno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 669.234:544.52(043.2) 171099395 MAG_Ostir_Andraz_2023.pdf MAG_Ostir_Andraz_2023.pdf 1 3679CB4E5F16168D28EB8C59F8872843 2310800ed609c76f7643e3919c9675f0ef6e6e1156018f2763bd21090b8dcd8a 0523900f-61c8-11ee-b28b-00155d000105 https://dk.um.si/Dokument.php?lang=slv&id=173251 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0