Light-induced palladium-catalyzed Buchwald Hartwig amination

master's thesis

Aljaž Oštir (Author), Peter Krajnc (Mentor), Lucas J. Goossen (Co-mentor)

Abstract

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.

Keywords

Buchwald-Hartwig amination;photochemistry;palladium;room temperature;ammonium salt;

Data

Language:	English
Year of publishing:	2023
Typology:	2.09 - Master's Thesis
Organization:	UM FKKT - Faculty of Chemistry and Chemical Engineering
Publisher:	[A. Oštir]
UDC:	669.234:544.52(043.2)
COBISS:	171099395
Views:	325
Downloads:	38
Average score:	0 (0 votes)
Metadata:

Other data

Secondary language:	Slovenian
Secondary title:	Svetlobno inducirana s paladijem katalizirana Buchwald-Hartwig aminacija
Secondary abstract:	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.
Secondary keywords:	Buchwald-Hartwig aminacija;fotokemija;paladij;sobna temperatura;amonijeva sol;magistrske naloge;
Type (COBISS):	Master's thesis/paper
Thesis comment:	Univ. v Mariboru, Fak. za kemijo in kemijsko tehnologijo
Pages:	1 spletni vir (1 datoteka PDF (XII, 45 f.))
ID:	19929258