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Pregled bibliografske jedinice broj: 1016860

Photochemical dehydration and deamination of phenols to quinone methides


Basarić, Nikola
Photochemical dehydration and deamination of phenols to quinone methides // First International Conference on Excited State Aromaticity and Antiaromaticity – ICESAA / Sigtuna, Švedska
Sigtuna, Švedska, 2019. str. IL-10 (pozvano predavanje, međunarodna recenzija, sažetak, znanstveni)


Naslov
Photochemical dehydration and deamination of phenols to quinone methides

Autori
Basarić, Nikola

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

Izvornik
First International Conference on Excited State Aromaticity and Antiaromaticity – ICESAA / Sigtuna, Švedska / - , 2019, IL-10

Skup
First International Conference on Excited State Aromaticity and Antiaromaticity / ICESAA - Sigtuna, Sweden

Mjesto i datum
Sigtuna, Švedska, 30.07-02.08.2019

Vrsta sudjelovanja
Pozvano predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
Antiaromatic excited state ; photodehydration ; photodeamination ; quinone methide

Sažetak
Quinone methides (QMs) are important intermediates in the reactions of phenols[1] that attracted scientific interest owing to their biological activity.[2] Some anticancer antibiotics exert they antiproliferative action based on intracellular formation of QMs. However, QMs are usually reactive species characterized by short lifetimes. Therefore, they have to be prepared in situ. Photochemical methods to generate QMs represent mild approach, particularly appealing in biological system. The most common photochemical reactions to generate QMs rely on dehydration[3] or deamination of suitably substituted phenols.[4] For the application of QMs in biology it is pivotal to fully unravel reaction mechanism of their formation. We have recently undertaken experimental and computational study to elucidate photodehydration mechanism of o-hydroxymethylphenol (1) that delivers QM.[5] Upon excitation, antiaromatic character of 1 (S1) provides a driving force on the S1 potential energy surface towards QM that is non-aromatic. Therefore, QM is formed in an ultrafast adiabatic photochemical reaction. A similar mechanistic scenario takes place for the deamination of 2, where the corresponding QM is formed in an ultrafast adiabatic photochemical reaction taking place very efficiently.[6] Furthermore, for applications in biology, it is important to extend the chromophoric system and excite molecule with visible light. Therefore, we incorporated QM precursors into structure of BODIPY chromophores, such as 3.[7] Upon excitation of these BODIPY-QM precursor molecules to S1, photodeamination does not take place due to an energy barrier on the S1 potential energy surface. However, excitation to higher excited singlet states provides QMs with BODIPY chromophore.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Projekt / tema
HRZZ-IP-2014-09-6312 - Supramolekulska kontrola fotokemijskih reakcija eliminacije (Nikola Basarić, )

Ustanove
Institut "Ruđer Bošković", Zagreb

Autor s matičnim brojem:
Nikola Basarić, (250000)