Naslov
Mechanistic study of mechanochemical regioselective halogenation of aromatic C–H bond with PdII catalysts

Autori
Barišić, Dajana ; Halasz, Ivan ; Bjelopetrović, Alen ; Babić, Darko ; Ćurić, Manda

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
27th Croatian Meeting of Chemists and Chemical Engineers and 5th Symposium Vladimir Prelog : Book of Abstracts / Marković, Dean ; Meštrović, Ernest ; Namjesnik, Danijel ; Tomašić, Vesna - Zagreb : Hrvatsko kemijsko društvo, 2021, 185-185

Skup
27. hrvatski skup kemičara i kemijskih inženjera (27HSKIKI) ; 5. simpozij Vladimir Prelog

Mjesto i datum
Veli Lošinj, Hrvatska, 05.10.2021. - 08.10.2021

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
Mechanochemistry ; halogenation ; catalysis ; mechanism

Sažetak
Organohalides are very valuable synthetic precursors, and the transformation of carbon- halogen (C–X) bond is often one of the synthetic steps in the preparation of numerous organic and natural compounds, pharmaceutically active substances, and new materials. Their preparation is traditionally limited to solvent-based synthetic procedures, and nowadays solid-state synthetic methods are increasingly being developed as their greener alternative, with mechanochemical reactions being the most prominent. Within this work, a mechanochemical procedure for regioselective halogenation of azobenzene C-H bond using PdII catalyst has been developed and optimized. The mechanism of this process has been studied by in situ Raman spectroscopy accompanied by ex situ NMR and PXRD experiments. A strong effect of solid and liquid additives on the reactivity of the catalytically active PdII species and intermediates has been established. Several possible palladacyclic intermediates have been synthesized and characterized, and their role in palladium-catalyzed ortho-halogenation of aromatic substrates has been discussed. Based on our results, a multistep reaction mechanism of this transformation has been proposed.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA