Naslov
Experimental and Computational Study of Regioselective Ferrocenoylation of Pyrimidine Nucleobases

Autori
Vrček, Valerije ; Šakić, Davor ; Havaić, Valentina ; Sanković, Krešimir ; Lapić, Jasmina ; Djaković, Senka

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

Izvornik
15th European Symposium of Organic Reactivity, Book of Abstract / Reiner Harges - Kiehl, 2015, 187-187

Skup
15th European Symposium of Organic Reactivity

Mjesto i datum
Kiel, Njemačka, 31.08.2015. - 04.09.2015

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
DFT; ferrocene; nucleoside; NMR

Sažetak
Uracil, thymine, and 5-fluorouracil (5-FU) have been ferrocenoylated selectively at N1-position. Deprotonated pyrimidine nucleobases, prepared by sodium hydride (NaH) in dimethylformamide (DMF), reacted with ferrocenoyl chloride (FcCOCl), or ferrocenoyl ethyl carbonate (FcCOOCOOEt), in DMF to obtain a single product. Regioselectivity of these reactions have been analyzed in details by NMR spectroscopy and quantum chemical calculations. 1H and 19F NMR spectra of reaction mixtures, and 13C NMR and 2D NOESY spectra of products, confirm the formation of the N1-isomer only. The calculated energy barrier for acetylation at N3-position is significantly higher (> 40 kJ/mol), which suggests that the analogous reaction at N1-position is kinetically controlled. The nucleophilic addition of pyrimidine bases to the carbonyl group of FcCOCl proceeds by a concerted SN2-like mechanism with the absence of the generally assumed tetrahedral intermediate.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA