Reaction mechanism of asymmetric catalysts by mass spectrometry and gas-phase vibrational ion spectroscopy

• Grant number: 14/15962-5
• Support Opportunities: Research Grants - Young Investigators Grants
• Start date: May 01, 2015
• End date: June 30, 2020
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Thiago Carita Correra
• Grantee: Thiago Carita Correra
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Associated researchers: Jose Manuel Riveros Nigra
• Associated research grant(s): 21/06726-0 - Investigation of reactive intermediates in complex chemical and biochemical processes, AP.JP2; 15/08539-1 - Multi-User Equipment approved in grant 2014/15962-5: ion trap mass spectrometer modified to perform infrared vibrational spectroscopy (IRMPD), AP.EMU
• Associated scholarship(s): 20/08894-4 - Mechanistic characterization of organometallic reactions by nonconventional sampling techniques in mass spectrometry, BP.DD; 19/22047-5 - Mechanistic evaluation of carbodiimides by mass spectrometry, BP.MS; 19/12808-9 - Glyphosate protonation and metal coordination sites, BP.IC; + associated scholarships 17/20262-0 - Unraveling electrochemical reaction intermediates by mass spectrometry coupled to ion vibrational spectroscopy, BP.PD; 17/18485-1 - Mechanistic studies of haloamination reactions promoted by metallic and organic catalysts, BP.DR; 17/22441-0 - Ion trap mass spectrometer modified to perform infrared vibrational spectroscopy, BP.TT; 16/19698-6 - Instrumental development for mechanistic studies, BP.MS; 15/11769-9 - Isolation of Sharpless reaction intermediates epoxidation and characterization of these species by theoretical calculations, BP.IC - associated scholarships

Abstract

This project intends to evaluate the reaction mechanisms of catalysts both in condensed and in the gas phase experimentally, by the use of mass spectrometry techniques like reaction intermediate fishing and vibrational ion spectroscopy (IRMPD), which is unprecedented in Brazil.IRMPD spectroscopy consists on the evaluation of ion dissociation in the gas phase promoted by a tunable infrared radiation, which is proportional to the absorption of energy at a given wavelength. The infrared spectrum obtained by this technique can be used to evaluate the conformational equilibrium and connectivity of ions, tasks that cannot be carried out by ordinary mass to charge ratio (m/z) measurements.The target systems of this proposal will be: i) the metal center catalysts, of which the Sharpless chiral reaction mediated by titanium alkoxides and chiral tartrates will be the first system to be evaluated, ii) the coordination of metal and model ligands, allowing the evaluation of the pre-catalyst assembly and activation in solution and, iii) the evaluation of organocatalysts and their reaction intermediates, like the iminium based MacMillan's imidazolidinones.Instrumentation design also plays an important role in this project, once the infrared ion spectroscopy in the gas phase is not available in commercial instruments and is, in fact, a novel technique in BrazilThis project will be supported by varied theoretical calculation methodologies, allowing the evaluation of conformer stabilities and reaction energy landscapes, giving a detailed picture of the systems in the molecular level.This proposal aims to elucidate the reaction mechanism of diverse catalysts by the synergic use of a novel technique and theoretical calculations, not only allowing the description of important reactions mechanism for widespread catalysts, but also helping in the development of new reactions and catalysts. (AU)

Scientific publications

(23)

(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)

PENNA, TATIANA C.; CERVI, GUSTAVO; RODRIGUES-OLIVEIRA, ANDRE F.; YAMADA, BRUNO D.; LIMA, RAFAEL Z. C.; MENEGON, JAIR J.; BASTOS, ERICK L.; CORRERA, THIAGO C.. Development of a photoinduced fragmentation ion trap for infrared multiple photon dissociation spectroscopy. RAPID COMMUNICATIONS IN MASS SPECTROMETRY, FEB 2020. (14/15962-5, 15/08539-1, 16/19698-6, 19/06391-8, 17/20262-0, 18/20592-3)

TAVARES, LAIS C.; PENNA, TATIANA C.; JOHNSON, MARK; CORRERA, THIAGO C.. Evaluation of protonation sites in two MacMillan catalysts in solution by gas phase predissociation spectroscopy and electronic structure calculations. ARKIVOC, n. 2, p. 134+, 2020. (14/15962-5, 17/20262-0, 15/08539-1)

BARBEIRO, CRISTIANE S.; VASCONCELOS, STANLEY N. S.; ZUKERMAN-SCHPECTOR, JULIO; CARACELLI, IGNEZ; PIMENTA, DANIEL C.; RODRIGUES, ANA CLARA B.; FERNANDES, ANDRE S.; CORRERA, THIAGO C.; BASTOS, ERICK L.; STEFANI, HELIO A.. Chlorinated 2-hydroxynaphthalenoxazolines: Synthesis, Reaction Mechanism and Fluorescence Properties. CHEMISTRYSELECT, v. 1, n. 18, p. 5647-5652, NOV 1 2016. (13/17960-7, 14/15962-5, 15/11769-9)

RODRIGUES-OLIVEIRA, ANDRE F.; RIBEIRO, FRANCISCO W. M.; CERVI, GUSTAVO; CORRERA, THIAGO C.. Evaluation of Common Theoretical Methods for Predicting Infrared Multiphotonic Dissociation Vibrational Spectra of Intramolecular Hydrogen-Bonded Ions. ACS OMEGA, v. 3, n. 8, p. 9075-9085, AUG 2018. (14/15962-5, 17/18485-1, 16/19698-6, 15/08539-1)

PRINCIVAL, CLEVERSON R.; ARCHILHA, MARCOS V. L. R.; DOS SANTOS, ALCINDO A.; FRANCO, MAURICIO P.; BRAGA, ATAUALPA A. C.; RODRIGUES-OLIVEIRA, ANDRE F.; CORRERA, THIAGO C.; CUNHA, RODRIGO L. O. R.; COMASSETO, JOAO V.. Stability Study of Hypervalent Tellurium Compounds in Aqueous Solutions. ACS OMEGA, v. 2, n. 8, p. 4431-4439, AUG 2017. (14/15962-5, 15/08539-1)

RODRIGUES-OLIVEIRA, ANDRE F.; BATISTA, PATRICK R.; DUCATI, LUCAS C.; CORRERA, THIAGO C.. Analyzing the N-H+center dot center dot center dot pi interactions of protonated tryptophan and phenylalkylamines using QTAIM, NCl, and NBO. THEORETICAL CHEMISTRY ACCOUNTS, v. 139, n. 8, JUL 14 2020. (19/25634-9, 14/15962-5, 15/08539-1, 18/07308-4)

TAVARES, LAIS C.; PENNA, TATIANA C.; JOHNSON, MARK; CORRERA, THIAGO C.. Evaluation of protonation sites in two MacMillan catalysts in solution by gas phase predissociation spectroscopy and electronic structure calculations. ARKIVOC, v. N/A, p. 23-pg., 2020-01-01. (17/20262-0, 15/08539-1, 14/15962-5)

PENNA, TATIANA C.; CERVI, GUSTAVO; RODRIGUES-OLIVEIRA, ANDRE F.; YAMADA, BRUNO D.; LIMA, RAFAEL Z. C.; MENEGON, JAIR J.; BASTOS, ERICK L.; CORRERA, THIAGO C.. Development of a photoinduced fragmentation ion trap for infrared multiple photon dissociation spectroscopy. RAPID COMMUNICATIONS IN MASS SPECTROMETRY, v. 34, p. 12-pg., 2020-02-08. (18/20592-3, 17/20262-0, 16/19698-6, 19/06391-8, 15/08539-1, 14/15962-5)

MASSON, MARIA ANGELICA C.; KARPFENSTEIN, RENAN; DE OLIVEIRA-SILVA, DIOGO; TEULER, JEAN-MARIE; ARCHIREL, PIERRE; MAITRE, PHILIPPE; CORRERA, THIAGO C.. Evaluation of Ca2+ Binding Sites in Tacrolimus by Infrared Multiple Photon Dissociation Spectroscopy. Journal of Physical Chemistry B, v. 122, n. 43, p. 9860-9868, NOV 1 2018. (15/08539-1, 14/15962-5)

BATISTA, PATRICK R.; PENNA, TATIANA C.; DUCATI, LUCAS C.; CORRERA, THIAGO C.. p-Aminobenzoic acid protonation dynamics in an evaporating droplet by ab initio molecular dynamics. Physical Chemistry Chemical Physics, v. 23, n. 35, AUG 2021. (17/20262-0, 20/10246-0, 19/25634-9, 18/07308-4, 15/08539-1, 14/15962-5)

CORRERA, THIAGO C.; FERNANDES, ANDRE S.; RIVEROS, JOSE M.. Dynamic/Thermochemical Balance Drives Unusual Alkyl/F Exchange Reactions in Siloxides and Analogs. Journal of Physical Chemistry A, v. 120, n. 10, p. 1644-1651, MAR 17 2016. (14/15962-5)

FERNANDES, ANDRE SANTOS; MAITRE, PHILIPPE; CORRERA, THIAGO CARITA. Evaluation of the Katsuki-Sharpless Epoxidation Precatalysts by ESI-FTMS, CID, and IRMPD Spectroscopy. Journal of Physical Chemistry A, v. 123, n. 5, p. 1022-1029, FEB 7 2019. (15/11769-9, 14/15962-5, 15/08539-1)

TRIPODI, GUILHERME L.; CORRERA, THIAGO C.; ANGOLINI, CELIO F. F.; FERREIRA, BRUNO R. V.; MAITRE, PHILIPPE; EBERLIN, MARCOS N.; ROITHOVA, JANA. The Intermediates in Lewis Acid Catalysis with Lanthanide Triflates. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2019, n. 22, p. 3560-3566, JUN 16 2019. (14/15962-5, 15/08539-1)

PAPA SPADAFORA, BRUNA; MOREIRA RIBEIRO, FRANCISCO WANDERSON; MATSUSHIMA, JULLYANE EMI; ARIGA, ELAINE MIHO; OMARI, ISAAC; SOARES, PRISCILA MACHADO ARRUDA; DE OLIVEIRA-SILVA, DIOGO; VINHATO, ELISANGELA; MCINDOE, J. SCOTT; CARITA CORRERA, THIAGO; et al. Regio- and diastereoselective Pd-catalyzed aminochlorocyclization of allylic carbamates: scope, derivatization, and mechanism. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 19, n. 25, JUN 2021. (19/16026-5, 16/21676-0, 15/08539-1, 16/17328-7, 17/18485-1, 14/15962-5, 19/25634-9)

ESTEVES, LARISSA C.; PINHEIRO, AMANDA C.; PIOLI, RENAN M.; PENNA, TATIANA C.; BAADER, WILHELM J.; CORRERA, THIAGO C.; BASTOS, ERICK L.. Revisiting the Mechanism of Hydrolysis of Betanin. Photochemistry and Photobiology, v. 94, n. 5, p. 853-864, SEP-OCT 2018. (15/18474-4, 14/22136-4, 15/08539-1, 14/15962-5, 16/21445-9)

TATIANA C. PENNA; THIAGO C. CORRERA. TÉCNICAS AVANÇADAS PARA A DIFERENCIAÇÃO DE ISÔMEROS POR ESPECTROMETRIA DE MASSAS. Química Nova, v. 43, n. 8, p. 1125-1137, 2020-10-16. (14/15962-5, 17/20262-0, 15/08539-1)

CORRERA, THIAGO CARITA; FERNANDES, ANDRE SANTOS; REGINATO, MARCELO MOTA; DUCATI, LUCAS COLUCCI; BERDEN, GIEL; OOMENS, JOS. Probing the geometry reorganization from solution to gas-phase in putrescine derivatives by IRMPD, H-1-NMR and theoretical calculations. Physical Chemistry Chemical Physics, v. 19, n. 35, p. 24330-24340, SEP 21 2017. (15/08541-6, 15/11769-9, 15/08539-1, 14/21930-9, 14/15962-5)

DE OLIVEIRA, ISADORA M.; VASCONCELOS, STANLEY S. N.; BARBEIRO, CRISTIANE S.; CORRERA, THIAGO C.; SHAMIM, ANWAR; PIMENTA, DANIEL C.; CARACELLI, IGNEZ; ZUKERMAN-SCHPECTOR, JULIO; STEFANI, HELIO A.; MANARIN, FLAVIA. Ytterbium(III)-catalyzed three-component reactions: synthesis of 4-organoselenium-quinolines. NEW JOURNAL OF CHEMISTRY, v. 41, n. 18, p. 9884-9888, SEP 21 2017. (13/17960-7, 12/00424-2, 14/15962-5, 16/04289-3)

SOUZA, DIEGO H. P.; GUIMARAES, ROBSON R.; CORRERA, THIAGO C.; ZAMARION, VITOR M.. Investigation of the photocatalytic activity of titanium dioxide films under visible light measured by electrospray mass spectrometry. NEW JOURNAL OF CHEMISTRY, v. 42, n. 22, p. 18259-18268, NOV 21 2018. (17/09469-2, 14/15962-5, 15/08539-1, 16/18354-1)

RIBEIRO, FRANCISCO W. M.; RODRIGUES-OLIVEIRA, ANDRE F.; CORRERA, THIAGO C.. Benzoxazine Formation Mechanism Evaluation by Direct Observation of Reaction Intermediates. Journal of Physical Chemistry A, v. 123, n. 38, p. 8179-8187, SEP 26 2019. (14/15962-5, 15/08539-1, 17/18485-1)

FERNANDES, ANDRE S.; OBEID, GUILHERME; LAURENO, TIAGO J. N.; CORRERA, THIAGO C.. Protonated and Sodiated Cyclophosphamide Fragmentation Pathways Evaluation by Infrared Multiple Photon Dissociation Spectroscopy. Journal of Physical Chemistry A, v. N/A, p. 10-pg., 2023-06-07. (15/08539-1, 19/25634-9, 20/08894-4, 21/06726-0, 14/15962-5)

OBEID, GUILHERME; MORAES, GUSTAVO O.; PENNA, TATIANA C.; SCHENBERG, LEONARDO A.; DUCATI, LUCAS C.; CORRERA, THIAGO C.. Solvation effects on glyphosate protonation and deprotonation states evaluated by mass spectrometry and explicit solvation simulations. Journal of Chemical Physics, v. 158, n. 5, p. 12-pg., 2023-02-07. (20/10246-0, 19/12808-9, 17/20262-0, 17/17750-3, 15/08539-1, 19/18727-0, 19/25634-9, 20/08894-4, 21/06726-0, 14/15962-5)

RIBEIRO, FRANCISCO W. M.; OMARI, ISAAC; THOMAS, GILIAN T.; PAUL, MATHIAS; WILLIAMS, PETER J. H.; MCINDOE, J. SCOTT; CORRERA, THIAGO C.. Microstructural Analysis of Benzoxazine Cationic Ring-Opening Polymerization Pathways. MACROMOLECULAR RAPID COMMUNICATIONS, v. N/A, p. 7-pg., 2023-10-09. (21/06726-0, 17/18485-1, 23/01180-4, 22/00498-8, 19/25634-9, 19/16026-5, 15/08539-1, 14/15962-5)