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
• City of the host institution: São Paulo
• 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 - 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

(25)

(The scientific publications listed on this page originate from the Web of Science or SciELO databases. Their authors have cited FAPESP grant or fellowship project numbers awarded to Principal Investigators or Fellowship Recipients, whether or not they are among the authors. This information is collected automatically and retrieved directly from those bibliometric databases.)

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)

TATIANA C. PENNA; THIAGO C. CORRERA. . Química Nova, v. 43, n. 8, p. 1125-1137, 2020-10-16. (17/20262-0, 15/08539-1, 14/15962-5)

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)

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)

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)

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)

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)

RIBEIRO, FRANCISCO WANDERSON MOREIRA; MATSUSHIMA, JULLYANE EMI; OBEID, GUILHERME; VINHATO, ELISANGELA; RODRIGUES, ALESSANDRO; CORRERA, THIAGO CARITA. Mechanistic Investigation of an Organocatalytic Bromocyclization of O-Allyl Carbamates. CHEMCATCHEM, v. 17, n. 8, p. 10-pg., 2025-03-16. (19/25634-9, 21/06726-0, 17/18485-1, 14/15962-5, 15/08539-1, 23/01180-4, 20/08894-4, 22/00498-8, 16/21676-0)

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)

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)

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)

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)

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)

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)

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)

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)

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)

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)

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)

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)

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)

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)

RIBEIRO, FRANCISCO W. M.; OMARI, ISAAC; MCINDOE, J. SCOTT; CORRERA, THIAGO C.. Protonation Effects on the Benzoxazine Formation Pathways and Products Distribution. ChemPhysChem, v. 25, n. 19, p. 214-pg., 2024-07-30. (19/25634-9, 17/18485-1, 21/06726-0, 14/15962-5, 22/00498-8, 23/01180-4, 15/08539-1, 19/16026-5)