Interpretation of substituent effects on 13C and 15N NMR chemical shifts in 6-substituted purines

STANDARA, Stanislav, Kateřina BOUZKOVÁ, Michal STRAKA, Zuzana ZACHAROVÁ, Michal HOCEK, Jaromír MAREK and Radek MAREK. Interpretation of substituent effects on 13C and 15N NMR chemical shifts in 6-substituted purines. Physical Chemistry Chemical Physics. Royal Society of Chemistry, 2011, vol. 13, No 35, p. 15854-15864. ISSN 1463-9076. Available from: https://dx.doi.org/10.1039/c1cp20680j.

Basic information

• Original name: Interpretation of substituent effects on 13C and 15N NMR chemical shifts in 6-substituted purines
• Authors: STANDARA, Stanislav (203 Czech Republic, belonging to the institution), Kateřina BOUZKOVÁ (203 Czech Republic, belonging to the institution), Michal STRAKA (203 Czech Republic), Zuzana ZACHAROVÁ (703 Slovakia, belonging to the institution), Michal HOCEK (203 Czech Republic), Jaromír MAREK (203 Czech Republic, belonging to the institution) and Radek MAREK (203 Czech Republic, guarantor, belonging to the institution).
• Edition: Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2011, 1463-9076.

Other information

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10403 Physical chemistry
• Country of publisher: United Kingdom of Great Britain and Northern Ireland
• Confidentiality degree: is not subject to a state or trade secret
• WWW: DOI: 10.1039/c1cp20680j
• Impact factor: Impact factor: 3.573
• RIV identification code: RIV/00216224:14740/11:00052846
• Organization unit: Central European Institute of Technology
• Doi: http://dx.doi.org/10.1039/c1cp20680j
• UT WoS: 000294167700016
• Keywords in English: Purine; Nuclear magnetic shielding; Localized molecular orbitals; Conformational dependence
• Tags: ok, rivok
• Tags: International impact, Reviewed

Abstract

The present work aims to analyze the effects of substituents on the electron distribution in the purine core as reflected by NMR chemical shifts. We collected a comprehensive set of experimental NMR data for a variety of 6-substituted purines and determined the molecular and crystal structures of three derivatives by X-ray diffraction. The density-functional methods have been employed to enable understanding of the substituent-induced changes in the NMR chemical shifts of the atoms in the purine skeleton. Analyses of the nuclear shielding using localized molecular orbitals (LMOs) were used to break down the values of the isotropic 13C and 15N NMR chemical shifts and the chemical shift tensors into the contributions of the individual LMOs. The experimental and calculated trends in the chemical shift of the N-3 atom correlate nicely with the Hammett constants and the calculated natural charges on N-3, whereas the contributions of the LMOs to the N-1 and C-6 chemical shifts are found to be more complex.

Links

• ED1.1.00/02.0068, research and development project: Name: CEITEC - central european institute of technology
• LC06030, research and development project: Name: Biomolekulární centrum

Investor: Ministry of Education, Youth and Sports of the CR, Biomolecular centre

• MSM0021622410, plan (intention): Name: Fyzikální a chemické vlastnosti pokročilých materiálů a struktur

Investor: Ministry of Education, Youth and Sports of the CR, Physical and chemical properties of advanced materials and structures

• MSM0021622413, plan (intention): Name: Proteiny v metabolismu a při interakci organismů s prostředím

Investor: Ministry of Education, Youth and Sports of the CR, Proteins in metabolism and interaction of organisms with the environment