Physicochemical studies of fluorinated organic compounds: experimental and theoretical approaches

• Grant number: 18/03910-1
• Support Opportunities: Research Grants - Young Investigators Grants
• Start date: November 01, 2018
• End date: December 31, 2024
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Rodrigo Antonio Cormanich
• Grantee: Rodrigo Antonio Cormanich
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant(s): 19/24758-6 - Multi-User Equipment approved in grant 2018/03910-1: X-Pulse HF benchtop NMR system, AP.EMU; 19/20522-8 - Multi-User Equipment approved in grant 2018/03910-1: EasyMax 102 advanced automated reactor, AP.EMU; 19/05028-7 - Physico-chemical studies of organofluorine compounds: experimental and theoretical approaches, AV.EXT
• Associated scholarship(s): 23/15485-1 - Effects caused by fluorine on physical chemistry properties of amino acids and proteins, BP.IC; 23/05418-5 - Study of the geometry and physical-chemical properties of fluorinated polymers: PVF and PVDF, BP.IC; 22/13984-8 - Study of the geometry and physicochemical properties of fluorinated polymers: PVF and PVDF, BP.IC; + associated scholarships 21/09716-5 - Synthesis, physicochemical properties and crystal structure simulations of organofluorine compounds, BP.DD; 20/13525-8 - Study of helical vs zigzag geometry of perfluorinated compounds capable of forming intramolecular hydrogen bonds, BP.IC; 20/06536-3 - Fluorinase reactive substrate analysis, BP.MS; 19/21136-4 - Mechanistic studies for the evaluation of the Thorpe-Ingold effect of CF2 groups in intramolecular cyclization reactions, BP.MS; 19/03855-3 - Synthesis of fluorinated derivatives of thymol and carvacrol and study of their physico-chemical properties, BP.IC; 18/21979-9 - Physical organic chemistry studies of peroxides and dissulfides for the understanding of their properties and reactivities, BP.IC - associated scholarships

Abstract

It is proposed the physicochemical study of organofluorinated compounds, which include their synthesis and characterization and the monitoring of its reaction mechanisms with the integrated use of 1H, 13C and 19F NMR and infrared spectroscopy and theoretical calculations of electronic structure. With the aid of the jovem pesquisador project it will be possible to implement modern methods of investigation of organic reaction mechanisms, which are insipient in Brazil, by monitoring reactions in situ in the reaction flask itself. In addition, the approval of this project is essential for a consolidation of the new research group of studies of fluorinated organic compounds that are intended to start at the IQ-UNICAMP, whose area is not studied in our country. For the present jovem pesquisador project, in which four master's scholarships are being requested, molecular systems were chosen for some case studies, which discuss very important aspects in constant discussion in the literature on physicochemical properties and reactivities of organofluorinated compounds and their applications. In the first case, it is intended to study the structure of fluorinated polymers in order to elucidate the effects that lead to their macroscopic physical-chemical properties. In the second case, we intend to investigate the mechanisms of reaction and the Thorpe-Ingold effect caused by the CF2 group in intramolecular cyclization reactions. A third project aim is to evaluate how the fluorine atom behaves as a proton receptor in intra- and intermolecular hydrogen bonds in fluorothiols. In the fourth project we intend to study the effect of CF2 groups on macrocycles such as crown ethers, which may have their interactions with ions increased relative to the non-fluorinated ones. The results obtained by the various experimental and theoretical methods applied here will be compared. In this way, it is expected that the integration of experimental and theoretical chemistries may help to highlight the obtained results and that both may help in the detailed descriptions of the results. In fact, it is expected to obtain complementary results between the various experimental and theoretical methods that will be applied and obtain results that none of them alone could achieve. Thus, the aim is to consolidate a new research group on the chemistry of fluorinated organic compounds and the investigation of reaction mechanisms at IQ-UNICAMP. The approval of this project will be extremely important in order to make it possible to implement the new experimental and theoretical methods that will be applied. Thus the present project of Jovem Pesquisador aims at the implementation of new lines of research and modern methods in mechanistic and structural studies of organic compounds. (AU)

Scientific publications

(34)

(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)

SILVA, DANIELA RODRIGUES; ZEOLY, LUCAS A.; VERMEEREN, PASCAL; CORMANICH, RODRIGO A.; HAMLIN, TREVOR A.; GUERRA, CELIA FONSECA; FREITAS, MATHEUS P.. Solvent effects on the sodium borohydride reduction of 2-halocyclohexanones. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, v. 36, n. 10, p. 8-pg., 2023-07-04. (18/03910-1)

HE, MENGFAN; PISCELLI, BRUNO A.; CORMANICH, RODRIGO A.; O'HAGAN, DAVID. Conformational Analysis Explores the Role of Electrostatic Nonclassical CFHC Hydrogen Bonding Interactions in Selectively Halogenated Cyclohexanes. Journal of Organic Chemistry, v. 89, n. 6, p. 10-pg., 2024-03-05. (23/14064-2, 18/03910-1)

LEPARFAIT, DAVID; THIERRY, THIBAULT; DA ROCHA, NICOLA L.; LEGAY, REMI; PFUND, EMMANUEL; CORMANICH, RODRIGO A.; LEQUEUX, THIERRY. Stereoselective Ring-Opening Reaction of α-Fluorinated Oxetanes: A Practical and Theoretical Investigation. Journal of Organic Chemistry, v. N/A, p. 13-pg., 2024-11-08. (18/03910-1)

DOBSON, LUCA S.; ZHANG, QINGZHI; MCKAY, BENJAMIN A.; OKE, OLUWAYINKA; ISANBOR, CHUKWUEMEKA; KHAN, MOHD FAHEEM; PISCELLI, BRUNO A.; CORDES, DAVID B.; CORMANICH, RODRIGO A.; MURPHY, CORMAC D.; et al. Aryl (ß,ß′,ß.-Trifluoro)-tert-butyl: A Candidate Motif for the Discovery of Bioactives. ORGANIC LETTERS, v. 25, n. 37, p. 6-pg., 2023-09-08. (22/10156-7, 18/03910-1)

MENEZES SPADETO, JOAO PAULO; FREITAS, MATHEUS P.; CORMANICH, RODRIGO A.. Fluorinated dihydropyridines as candidates to block L-type voltage-dependent calcium channels. JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS, v. 40, n. 24, p. 16-pg., 2022-01-01. (20/06536-3, 18/03910-1)

ANDRADE, LAIZE A. F.; ZEOLY, LUCAS A.; CORMANICH, RODRIGO A.; FREITAS, MATHEUS P.. Conformational signature of Ishikawa's reagent using NMR information from diastereotopic fluorines. Beilstein Journal of Organic Chemistry, v. 15, p. 506-512, FEB 20 2019. (18/03910-1)

ZHANG, HUAIYUAN; CORMANICH, RODRIGO A.; WIRTH, THOMAS. Chiral Ligands in Hypervalent Iodine Compounds: Synthesis and Structures of Binaphthyl-Based lambda(3)-Iodanes. CHEMISTRY-A EUROPEAN JOURNAL, DEC 2021. (18/03910-1)

SIMOES, LUIS H.; CORMANICH, RODRIGO A.. Stereoelectronic Effects in Multivicinal Fluoroalkanes and Conformational Implications. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2020, n. 4, JAN 2020. (18/03910-1)

PISCELLI, BRUNO A.; SANDERS, WILLIAM; YU, CIHANG; AL MAHARIK, NAWAF; LEBL, THOMAS; CORMANICH, RODRIGO A.; O'HAGAN, DAVID. Fluorine-Induced Pseudo-Anomeric Effects in Methoxycyclohexanes through Electrostatic 1,3-Diaxial Interactions. CHEMISTRY-A EUROPEAN JOURNAL, v. 26, n. 52, AUG 2020. (18/03910-1, 19/05028-7, 19/03855-3)

MENEZES SPADETO, JOAO PAULO; FREITAS, MATHEUS P.; CORMANICH, RODRIGO A.. Fluorinated dihydropyridines as candidates to block L-type voltage-dependent calcium channels. JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS, OCT 2021. (20/06536-3, 18/03910-1)

PISCELLI, BRUNO A.; O'HAGAN, DAVID; CORMANICH, RODRIGO A.. Contribution of Hyperconjugation and Inductive Effects to the Pseudo-anomeric Effect in 4-Substituted Methoxycyclohexanes. Journal of Physical Chemistry A, v. N/A, p. 5-pg., 2023-01-17. (18/03910-1, 21/09716-5)

TARUI, ATSUSHI; PISCELLI, BRUNO A.; AL-MAHARIK, NAWAF; STEWART, JOSEPHINE M.; NIEMCOVA, PATRICIE; CORDES, DAVID B.; MCKAY, AIDAN P.; MURPHY, CORMAC D.; CORMANICH, RODRIGO A.; HAGAN, DAVID O'. Synthesis and Analysis of (γ,γ',γ''-Trifluoro)neopentyl (TFNP) Aryl Ethers as a Polar Fluoroaliphatic Motif. CHEMISTRY-A EUROPEAN JOURNAL, v. 30, n. 57, p. 5-pg., 2024-09-24. (22/10156-7, 23/14064-2, 18/03910-1)

BEZERRA, JULIA N.; SPADETO, JOAO PAULO M.; DARE, JOYCE K.; ALMEIDA, WANDA PEREIRA; FREITAS, MATHEUS P.; CORMANICH, RODRIGO A.. In Silico Interactions of the Components from the Schinus terebinthifolius Extract with Human Tyrosinase. CHEMPLUSCHEM, v. 87, n. 8, p. 12-pg., 2022-08-01. (20/06536-3, 18/03910-1)

AFONSO, MARCO A. S.; CORMANICH, RODRIGO A.. The preferred geometry of hydroperoxides is the result of an interplay between electrostatic and hyperconjugative effects. Physical Chemistry Chemical Physics, v. 22, n. 46, p. 27173-27177, DEC 14 2020. (18/21979-9, 18/03910-1)

DE GIOVANETTI, MARINELLA; FERRAZ BITENCOURT, LUIS FELIPE; CORMANICH, RODRIGO; SAUER, STEPHAN P. A.. n the Unexpected Accuracy of the M06L Functional in the Calculation of (1)J(FC) Spin-Spin Coupling Constant. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, v. 17, n. 12, p. 7712-7723, DEC 14 2021. (18/03910-1, 19/24788-2)

STIVANIN, MATEUS L.; GALLO, RAFAEL D. C.; SPADETO, JOAO PAULO M.; CORMANICH, RODRIGO A.; JURBERG, IGOR D.. visible light-mediated three-component strategy based on the ring-opening of cyclic ethers with aryldiazoacetates and nucleophile. ORGANIC CHEMISTRY FRONTIERS, v. 9, n. 5, p. 1321-1326, MAR 1 2022. (20/00144-6, 20/06536-3, 18/03910-1, 19/01235-8)

SPADETO, JOAO P. M.; CORMANICH, RODRIGO A.; FRANCA, TANOS C. C.; LAPLANTE, STEVEN R.; GONCALVES, ARLAN S.. Docking and molecular dynamics studies of potential new leads against DBL3x derived from chondroitin sulfate A (CSA): a new approach for the treatment of malaria. JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS, APR 2021. (18/03910-1, 20/06536-3)

ZEOLY, LUCAS A.; COELHO, FERNANDO; CORMANICH, RODRIGO A.. Intramolecular H-Bond Is Formed in 2-Fluorophenol and 2-Fluorothiophenol, but It May Not Be the Main Pathway of the J(FH) Coupling Constant Transmission. Journal of Physical Chemistry A, v. 123, n. 46, p. 10072-10078, NOV 21 2019. (18/03910-1)

PISCELLI, BRUNO A.; O'HAGAN, DAVID; CORMANICH, RODRIGO A.. The contribution of non-classical CHaxMIDLINE HORIZONTAL ELLIPSISOC hydrogen bonds to the anomeric effect in fluoro and oxa-methoxycyclohexanes. Physical Chemistry Chemical Physics, v. 23, n. 10, p. 5845-5851, MAR 14 2021. (18/03910-1, 19/03855-3, 19/05028-7)

DE GIOVANETTI, MARINELLA; CORMANICH, RODRIGO A.; SAUER, STEPHAN P. A.. On the Performance of Second-Order Polarization Propagator Methods in the Calculation of ¹J_FC and ⁿJ_FH NMR Spin-Spin Coupling Constants. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, v. N/A, p. 15-pg., 2024-11-29. (18/03910-1)

POSKIN, THOMAS J.; PISCELLI, BRUNO A.; MCKAY, AIDAN P.; CORDES, DAVID B.; EGUCHI, YUTO; YAMADA, SHIGEYUKI; CORMANICH, RODRIGO A.; O'HAGAN, DAVID. Synthesis of Janus All-Cis Tetrafluorocyclohexanes Carrying 1,4-Diether Motifs. Journal of Organic Chemistry, v. N/A, p. 7-pg., 2024-11-27. (22/10156-7, 23/14064-2, 18/03910-1)

GARRISON, NATHANIEL G.; HARRY, STEFAN ANDREW; SIEGLER, MAXIME A.; CARIELLO, GUILHERME; CORMANICH, RODRIGO A.; LECTKA, THOMAS. The C-F⋅⋅⋅H-CF₂ interaction: A combination of hydrogen bonding and n → σ* stabilization. JOURNAL OF FLUORINE CHEMISTRY, v. 272, p. 7-pg., 2023-10-19. (18/03910-1)

PORT, VINICIUS C.; ZEOLY, LUCAS A.; COELHO, FERNANDO; CORMANICH, RODRIGO A.. Through space J(FH) spin-spin coupling constant transmission pathways in 2-(trifluoromethyl)thiophenol: formation of unusual stabilizing bifurcated CF center dot center dot center dot HS and CF center dot center dot center dot SH interactions. Physical Chemistry Chemical Physics, v. 23, n. 15, p. 9-pg., 2021-04-21. (18/03910-1)

CORMANICH, RODRIGO A.; ZEOLY, LUCAS A.; SANTOS, HUGO; CAMILO, NILTON S.; BUHL, MICHAEL; COELHO, FERNANDO. Origin of the Diastereoselectivity of the Heterogeneous Hydrogenation of a Substituted Indolizine. Journal of Organic Chemistry, v. 85, n. 17, p. 8-pg., 2020-09-04. (13/07600-3, 18/03910-1, 15/09205-0)

SIMOES, LUIS H.; CORMANICH, RODRIGO A.. Challenges in studying steric interactions in highly strained perhalogenated alkanes and silanes. International Journal of Quantum Chemistry, v. 121, n. 21, AUG 2021. (18/03910-1)

CLARK, JOSHUA L.; TAYLOR, ALARIC; GEDDIS, AILSA; NEYYAPPADATH, RIFAHATH M.; PISCELLI, BRUNO A.; YU, CIHANG; CORDES, DAVID B.; SLAWIN, ALEXANDRA M. Z.; CORMANICH, RODRIGO A.; GULDIN, STEFAN; et al. Supramolecular packing of alkyl substituted Janus face all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs. CHEMICAL SCIENCE, v. 12, n. 28, p. 9712-9719, JUL 28 2021. (18/03910-1, 19/03855-3)

PORT, VINICIUS C.; CORMANICH, RODRIGO A.. There and back again: the role of hyperconjugation in the fluorine gauche effect. Physical Chemistry Chemical Physics, v. 23, n. 32, JUL 2021. (18/03910-1)

DA SILVA, AMANDA F.; AFONSO, MARCO A. S.; CORMANICH, RODRIGO A.; JURBERG, IGOR D.. Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation. CHEMISTRY-A EUROPEAN JOURNAL, v. 26, n. 25, MAR 2020. (18/03910-1, 18/21979-9, 17/24017-0)

GOMES, GUSTAVO R.; SCOPEL, EUPIDIO; ROCHA, NICOLA L.; BREITKREITZ, MARCIA C.; CORMANICH, RODRIGO A.; REZENDE, CAMILA A.; PASTRE, JULIO C.. Direct Ethyl Levulinate Production from Raw Lignocellulosic Biomass Mediated by a Novel Taurine-Based Imidazolium Ionic Liquid. ACS SUSTAINABLE CHEMISTRY & ENGINEERING, v. N/A, p. 13-pg., 2022-11-21. (18/23769-1, 18/09861-2, 14/26378-2, 18/03910-1, 21/06661-5, 19/19360-3, 14/25770-6, 20/11578-7)

FERNANDES, ALESSANDRA A. G.; DA SILVA, AMANDA F.; OKADA, JR., CELSO Y.; SUZUKAWA, VITOR; CORMANICH, RODRIGO A.; JURBERG, IGOR D.. General Platform for the Conversion of Isoxazol-5-ones to 3,5-Disubstituted Isoxazoles via Nucleophilic Substitutions and Palladium Catalyzed Cross-Coupling Strategies. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2019, n. 19, p. 3022-3034, MAY 26 2019. (17/22164-6, 17/24017-0, 18/03910-1)

CARIELLO, GUILHERME; ZEOLY, LUCAS A.; PISCELLI, BRUNO A.; LECTKA, THOMAS; CORMANICH, RODRIGO A.. The pitfalls of using J_HF spin-spin coupling constants to infer hydrogen bond formation in organofluorine compounds. CHEMICAL COMMUNICATIONS, v. 59, n. 99, p. 4-pg., 2023-11-15. (23/14064-2, 22/16188-8, 18/03910-1)

SPADETO, JOAO P. M.; CORMANICH, RODRIGO A.; FRANCA, TANOS C. C.; LAPLANTE, STEVEN R.; GONCALVES, ARLAN S.. Docking and molecular dynamics studies of potential new leads against DBL3x derived from chondroitin sulfate A (CSA): a new approach for the treatment of malaria. JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS, v. 40, n. 18, p. 10-pg., 2021-04-05. (18/03910-1, 20/06536-3)

CORMANICH, RODRIGO A.; DA SILVA, GABRIEL D.. Autobench V1.0: Benchmarking Automation for Electronic Structure Calculations. JOURNAL OF CHEMICAL INFORMATION AND MODELING, v. 64, n. 8, p. 10-pg., 2024-03-27. (20/13525-8, 18/03910-1)

YU, CIHANG; PISCELLI, BRUNO A.; AL MAHARIK, NAWAF; CORDES, DAVID B.; SLAWIN, ALEXANDRA M. Z.; CORMANICH, RODRIGO A.; O'HAGAN, DAVID. Unexpected triaxial preferences in some all-syn 1,3,5-trifluorocyclohexanes. CHEMICAL COMMUNICATIONS, v. 58, n. 92, p. 4-pg., 2022-10-25. (18/03910-1, 21/09716-5)