Conformational equilibria studies by nuclear magnetic resonance spectroscopy, infrared spectroscopy and theoretical calculations

• Grant number: 05/59649-0
• Support Opportunities: Research Projects - Thematic Grants
• Duration: June 01, 2006 - May 31, 2011
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Roberto Rittner Neto
• Grantee: Roberto Rittner Neto
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Pesquisadores principais: Paulo Roberto Olivato
• Associated grant(s): 07/51146-4 - A theoretical study of the effects of substituents on 3jch nmr coupling in alpha-substituted acetamides., AR.BR
• Associated scholarship(s): 09/07765-7 - Experimental and theoretical studies of nJCH coupling constants, BP.PD; 09/02715-1 - NMR spectroscopy and theoretical calculations in the conformational analysis of some essential aminoacids and their N-acetylated derivatives, BP.MS

Abstract

This project aims the study of the several properties and of the distinct types of interactions which rule the stability of a given molecular conformation and, consequently, are responsible for the macroscopic properties of the corresponding substance. In order to achieve these objectives the conformational equilibria of several selected model compounds and some relevant biologically active compounds will be investigated, and the important effects as anomeric, hyperconjugative, gauche and intramolecular hydrogen bonds will be examined too. Priority will be given to the study of sulphur, nitrogen and phosphorus compounds, 5 and 6-membered ring alicyclic compounds and aminoacids and neurotransmitters. Conformational analyses will be performed through the methodology previously developed in our laboratories, as the main objective of the previous thematic project (00/07692-5), which involves experimental data from infrared and nuclear magnetic resonance spectra, the solvation theory and theoretical calculations of the geometries and energies of the main conformers existing in the studied equilibria. The electronic interactions will be investigated through the coupling constants experimental and calculated values and by using data from NBO (Natural Bond Orbital) method calculations. NMR spectrometers (Varian Gemini-300; Bruker AC-300P e Varian INOVA-500) and infrared spectrometers (Bomem MB-1OO e Bomem DA-08) are available at this department, for performing the proposed experiments. A reparative HPLC has been included in this application for the separation and purification of 'he target compounds, which will be synthesized in our laboratories, as well some personal computers, to reinforce the actual assemble already existent for the theoretical calculations. (AU)

Scientific publications

(27)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

CONTRERAS, RUBEN H.; DOS SANTOS, FRANCISCO P.; DUCATI, LUCAS C.; TORMENA, CLAUDIO F.. Difference between (2)J(C2H3) and (2)J(C3H2) spin-spin couplings in heterocyclic five- and six-membered rings as a probe for studying sigma-ring currents: a quantum chemical analysist. Magnetic Resonance in Chemistry, v. 48, n. 1, p. S151-S158, DEC 2010. (08/06282-0, 09/07765-7, 05/59649-0)

FRANCISCO P. DOS SANTOS; LUCAS C. DUCATI; CLÁUDIO F. TORMENA; ROBERTO RITTNER. Efeito das interações hiperconjugativas na constante de acoplamento ¹J CH da hexametilenotetramina e do adamantano: estudo teórico e experimental. Química Nova, v. 30, n. 7, p. 1681-1685, 2007-00-00. (05/59649-0)

MARTINS, CARINA R.; DUCATI, LUCAS C.; TORMENA, CLAUDIO F.; RITTNER, ROBERTO. Conformational analysis of 2-halocyclopentanones by NMR and IR spectroscopies and theoretical calculations. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 72, n. 5, p. 1089-1096, JUN 2009. (05/59649-0)

GAUZE, GISELE F.; BASSO, ERNANI A.; CONTRERAS, RUBEN H.; TORMENA, CLAUDIO F.. Effect of Sulfur Oxidation on the Transmission Mechanism of (4)J(HH) NMR Coupling Constants in 1,3-Dithiane. Journal of Physical Chemistry A, v. 113, n. 11, p. 2647-2651, MAR 19 2009. (05/59649-0)

CONTRERAS, RUBEN H.; PROVASI, PATRICIO F.; DOS SANTOS, FRANCISCO P.; TORMENA, CLAUDIO F.. Stereochemical dependence of NMR geminal spin-spin coupling constants. Magnetic Resonance in Chemistry, v. 47, n. 2, p. 113-120, FEB 2009. (05/59649-0)

VILCACHAGUA, JANAINA DANTAS; DUCATI, LUCAS C.; RITTNER, ROBERTO; CONTRERAS, RUBEN H.; TORMENA, CLAUDIO F.. Experimental, SOPPA(CCSD), and DFT Analysis of Substitutent Effects on NMR (1)J(CF) Coupling Constants in Fluorobenzene Derivatives. Journal of Physical Chemistry A, v. 115, n. 7, p. 1272-1279, FEB 24 2011. (05/59649-0)

ANTUNES, JOAO E.; FREITAS, MATHEUS P.; RITTNER, ROBERTO. Bioactivities of a series of phosphodiesterase type 5 (PDE-5) inhibitors as modelled by MIA-QSAR. EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY, v. 43, n. 8, p. 1632-1638, AUG 2008. (05/59649-0)

NETO‚ A.C.; SANTOS‚ F.P.; PAULA‚ A.S.; TORMENA‚ C.F.; RITTNER‚ R.. Density functionals for calculating NMR¹ J_CH coupling constants in electron-rich systems. Chemical Physics Letters, v. 454, n. 1, p. 129-132, 2008. (05/59649-0)

FREITAS‚ M.P.; RITTNER‚ R.. MIA-QSAR as an Alternative Approach for Modeling Some Antifungals. QSAR & COMBINATORIAL SCIENCE, v. 27, n. 5, p. 582-585, 2008. (05/59649-0)

PEDERSOLI‚ S.; LOMBARDI‚ L.; HÖEHR‚ N.F.; RITTNER‚ PROF. ROBERTO. Assignments of 1H and 13C NMR spectral data for benzoylecgonine‚ a cocaine metabolite. SPECTROSCOPY LETTERS, v. 41, n. 3, p. 101-103, 2008. (05/59649-0)

DE OLIVEIRA, ANDRE N.; BOCCA, CLEVERSON C.; CARVALHO, JOAO E.; RUIZ, ANA LUCIA G.; SILVA, THIAGO P.; RITTNER, ROBERTO; HOEHR, NELCI F.. New substituted 4-arylaminoquinazolines as potent inhibitors of breast tumor cell lines: In vitro and docking experiments. EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY, v. 45, n. 9, p. 4339-4342, SEP 2010. (05/59649-0)

BOCCA, CLEVERSON C.; RITTNER, ROBERTO; HOEEHR, NELCI F.; PINHEIRO, GLAUCIA M. S.; ABIKO, LAYARA A.; BASSO, ERNANI A.. Molecular modeling and biological evaluation of 2-N,N-dimethylaminecyclohexyl 1-N ',N '-dimethylcarbamate isomers and their methylsulfate salts as cholinesterases inhibitors. Journal of Molecular Structure, v. 983, n. 1-3, p. 6-pg., 2010-11-01. (05/59649-0)

BOCCA, CLEVERSON C.; RITTNER, ROBERTO; HOEEHR, NELCI F.; PINHEIRO, GLAUCIA M. S.; ABIKO, LAYARA A.; BASSO, ERNANI A.. Molecular modeling and biological evaluation of 2-N,N-dimethylaminecyclohexyl 1-N `,N `-dimethylcarbamate isomers and their methylsulfate salts as cholinesterases inhibitors. Journal of Molecular Structure, v. 983, n. 1-3, p. 194-199, NOV 1 2010. (05/59649-0)

ANIZELLI, PEDRO R.; VILCACHAGUA, JANAINA D.; CUNHA NETO, ALVARO; TORMENA, CLAUDIO F.. Stereoelectronic interaction and their effects on conformational preference for 2-substituted methylenecyclohexane: An experimental and theoretical investigation. Journal of Physical Chemistry A, v. 112, n. 37, p. 8785-8789, SEP 18 2008. (05/59649-0)

ANTUNES, JOAO E.; FREITAS, MATHEUS P.; DA CUNHA, ELAINE F. F.; RAMALHO, TEODORICO C.; RITTNER, ROBERTO. In silico prediction of novel phosphodiesterase type-5 inhibitors derived from Sildenafil, Vardenafil and Tadalafil. Bioorganic & Medicinal Chemistry, v. 16, n. 16, p. 7599-7606, AUG 15 2008. (05/59649-0)

BOCCA, CLEVERSON C.; RITTNER, ROBERTO; DA SILVA, ALAN P.; BASSO, ERNANI A.. Substituent effects on the reduction of 2-alkylcyclohexanones by LiAlH4: an investigation of conformational equilibria and transition states. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, v. 24, n. 3, p. 241-248, MAR 2011. (05/59649-0)

PEDERSOLI, SUSIMAIRE; TORMENA, CLAUDIO F.; DOS SANTOS, FRANCISCO P.; CONTRERAS, RUBEN H.; RITTNER, ROBERTO. Stereochemical behavior of (1)J(CH) and (2)J(CH) NMR coupling constants in alpha-substituted acetamides. Journal of Molecular Structure, v. 891, n. 1-3, p. 508-513, NOV 26 2008. (05/59649-0)

NETO, ALVARO CUNHA; DOS SANTOS, FRANCISCO P.; CONTRERAS, RUBEN H.; RITTNER, ROBERTO; TORMENA, CLAUDIO F.. Analysis of the Electronic Origin of the (1)J(CH) Spin-Spin Coupling Trend in 1-X-Cyclopropanes: Experimental and DFT Study. Journal of Physical Chemistry A, v. 112, n. 46, p. 11956-11959, NOV 20 2008. (05/59649-0)

TASIC, L.; RITTNER, R.. alpha-Substituent effects on C-13 NMR chemical shifts in some aliphatic compounds: Application of principal component analysis (PCA). Journal of Molecular Structure, v. 933, n. 1-3, p. 15-19, SEP 17 2009. (05/59649-0)

COELHO, JAKELYNE V.; FREITAS, MATHEUS P.; TORMENA, CLAUDIO F.; RITTNER, ROBERTO. On the (4)J(HH) long-range coupling in 2-bromocyclohexanone: conformational insights. Magnetic Resonance in Chemistry, v. 47, n. 4, p. 348-351, APR 2009. (05/59649-0)

FIORIN, BARBARA C.; BASSO, ERNANI A.; TORMENA, CLAUDIO F.; RITTNER, ROBERTO; ABRAHAM, RAYMOND J.. Theoretical and Experimental Investigation on the Rotational Isomerism in alpha-Fluoroacetophenones. Journal of Physical Chemistry A, v. 113, n. 12, p. 2906-2913, MAR 26 2009. (05/59649-0)

ROZADA, THIAGO C.; GAUZE, GISELE F.; FAVARO, DENIZE C.; RITTNER, ROBERTO; BASSO, ERNANI A.. Infrared and theoretical calculations in 2-halocycloheptanones conformational analysis. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 94, p. 277-287, AUG 2012. (05/59649-0)

TORMENA, CLAUDIO F.; LACERDA, JR., VALDEMAR; DE OLIVEIRA, KLEBER T.. Revisiting the stability of endo/exo Diels-Alder adducts between cyclopentadiene and 1,4-benzoquinone. Journal of the Brazilian Chemical Society, v. 21, n. 1, p. 112-118, 2010. (05/59649-0, 08/06619-4)

LLORET, GUSTAVO R.; CUNHA NETO, ALVARO; RITTNER, ROBERTO; BITENCOURT, MICHELLE; FREITAS, MATHEUS P.; AQUINO, NILTON S.. Synthesis and rational design of anti-inflammatory compounds: N-phenyl-cyclohexenyl sulfonamide derivatives. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, v. 22, n. 12, p. 1188-1192, DEC 2009. (05/59649-0)

DA SILVA, JULIO CESAR A.; DUCATI, LUCAS C.; RITTNER, ROBERTO. Conformational and stereoeletronic investigations of muscarinic agonists of acetylcholine by NMR and theoretical calculations. Journal of Molecular Structure, v. 1015, p. 33-40, MAY 16 2012. (05/59649-0, 09/54071-0)

CONTRERAS, RUBEN H.; DOS SANTOS, FRANCISCO P.; DUCATI, LUCAS C.; TORMENA, CLAUDIO F.. Difference between (2)J(C2H3) and (2)J(C3H2) spin-spin couplings in heterocyclic five- and six-membered rings as a probe for studying sigma-ring currents: a quantum chemical analysist. Magnetic Resonance in Chemistry, v. 48, p. 8-pg., 2010-12-01. (08/06282-0, 05/59649-0, 09/07765-7)

ABRAHAM, RAYMOND J.; LEONARD, PAUL; TORMENA, CLAUDIO F.. A H-1 NMR and theoretical investigation of the conformations of some monosubstituted cyclobutanes. Magnetic Resonance in Chemistry, v. 49, n. 1, p. 23-29, JAN 2011. (08/06282-0, 09/07765-7, 05/59649-0)