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Ferrocenoyl-Purines: Regioselective Synthesis and Acylation Mechanism (CROSBI ID 663352)

Prilog sa skupa u zborniku | sažetak izlaganja sa skupa | domaća recenzija

Toma, Mateja ; Filipović, Alma ; Lapić, Jasmina ; Djaković, Senka ; Šakić, Davor ; Vrček, Valerije Ferrocenoyl-Purines: Regioselective Synthesis and Acylation Mechanism // Computational Chemistry Day - Book of Abstracts / Babić, Darko (ur.). Zagreb: Prirodoslovno-matematički fakultet Sveučilišta u Zagrebu, 2018. str. 29-29

Podaci o odgovornosti

Toma, Mateja ; Filipović, Alma ; Lapić, Jasmina ; Djaković, Senka ; Šakić, Davor ; Vrček, Valerije

engleski

Ferrocenoyl-Purines: Regioselective Synthesis and Acylation Mechanism

Ferrocene nucleobase conjugates are organometallic compounds where the ferrocene moiety is covalently linked through various "linkers" with heterocyclic nucleobases. [1] The synthesis of ferrocenoyl-purines is based on acylation [2] of purine anions with ferrocenoyl-chloride and in most cases both N7- and N9- isomers were detected by NMR spectroscopy and isolated. In this study we combined synthesis, NMR spectroscopy and quantum chemical calculations to investigate the steric effect of C6-substituent of purine anions on N9/N7 ferrocenoylation. It is found that N9/N7-regioisomers ratio is dependent on the C6–substitution of the purine system. It is possible that the bulkier substituent at C6-position causes shielding of the N7 position which inhibits N7-acylation of purine anions. When adenine anion was ferrocenoylated, the N9-isomer was the major product (79%). For N6-methyl adenine and N6, N6-dimethyl adenine the acylation resulted in increased yield of N9-isomer, leading to reaction regiospecificity in case of the N(Boc)2-adenine where only N9-regioisemer was formed. The ratio of N9 : N7 isomers, determined quantitatively by integration of signals in 1H NMR spectra of the reaction mixture, is strongly correlated to the effective (Charton’s) and calculated multidimensional (Sterimol) steric parameters of the C6-substituent. Finally, quantum-chemical calculations suggest that the barrier for the N7-isomer formation is higher than the corresponding barrier for N9-isomer formation. The calculated energy barrier difference for N7 and N9 –acylation reaction is in correlation with N9/N7 product ratio andsteric parameters of C6-substituents, which nicely supports our experimental results . All structures were optimized with the B3LYP functional and the standard 6-31+G(d) basis set was used for geometry optimizations and frequency calculations.

ferrocene, nucleobase, DFT, acylation mechanism

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Podaci o prilogu

29-29.

2018.

objavljeno

Podaci o matičnoj publikaciji

Computational Chemistry Day - Book of Abstracts

Babić, Darko

Zagreb: Prirodoslovno-matematički fakultet Sveučilišta u Zagrebu

978-953-6076-45-1

Podaci o skupu

Computational Chemistry Day 2018

poster

12.05.2018-12.05.2018

Zagreb, Hrvatska

Povezanost rada

Kemija, Farmacija