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Mechanistic studies of haloamination reactions promoted by metallic and organic catalysts

Grant number: 17/18485-1
Support Opportunities:Scholarships in Brazil - Doctorate
Effective date (Start): December 01, 2017
Effective date (End): June 30, 2022
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal Investigator:Thiago Carita Correra
Grantee:Francisco Wanderson Moreira Ribeiro
Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
Associated research grant:14/15962-5 - Reaction mechanism of asymmetric catalysts by mass spectrometry and gas-phase vibrational ion spectroscopy, AP.JP
Associated scholarship(s):19/16026-5 - Cyclization reactions promoted by Pd/Cu Catalysts, BE.EP.DR


This project aim to study chiral haloamination reactions aiming the synthesis of aminodiol. The allylic alcohol and, overall, its structural analogs are organic compounds that attract great attention from the scientific community, as they can be used as starting reactants for a series of target products. Here, we intend to evaluate new versions of chiral intramolecular haloamination reactions of allylic alcohol analogs promoted by Paladium(II)/Copper(II) and organocatalysts. To achieve this goal, we will use a coupled mass spectrometry/vibrational ion spectroscopy (IRMPD) approach supported by theoretical calculations to survey and to propose a catalytic cycle for the metallic and organic catalyzed haloamination reactions. We aim to identify by experimental techniques the reactive intermediates which support the proposed reaction mechanism. Therefore, by the proposition of catalytic cycles, we intend to achieve a better understanding on the origins of the regio-, diastero- and enantioselectivity on the haloaminated product formed.On the experimental side, the reactions will be monitored by ESI-MS and the reaction intermediates will be characterized by their mass to charge ratio, fragmentation pattern and their infrared vibrational IRMPD spectraOn the theoretical side, we aim to use electronic structure models to describe the kinetic and thermodynamic behavior of the proposed mechanism.Besides that, conformational search methods will be used to allow the assignment of the acquired IRMPD spectra.We believe that this project will allow the characterization of the protonation and coordination sites of several catalytic species and reactants used on the target synthesis as also as other widespread reactions.This proposal will foster the understanding of the catalytic cycle of this important class of reaction and, therefore, the development of new catalysts and reaction conditions with expressive enhancement of the reaction performance.

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Scientific publications (4)
(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)
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, . (14/15962-5, 15/08539-1, 17/18485-1)
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., . (21/06726-0, 17/18485-1, 23/01180-4, 22/00498-8, 19/25634-9, 19/16026-5, 15/08539-1, 14/15962-5)
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, . (14/15962-5, 17/18485-1, 16/19698-6, 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, . (19/16026-5, 16/21676-0, 15/08539-1, 16/17328-7, 17/18485-1, 14/15962-5, 19/25634-9)
Academic Publications
(References retrieved automatically from State of São Paulo Research Institutions)
RIBEIRO, Francisco Wanderson Moreira. Study of catalytic reactions by action spectroscopy and ionic mobility coupled by mass spectrometry. 2022. Doctoral Thesis - Universidade de São Paulo (USP). Conjunto das Químicas (IQ e FCF) (CQ/DBDCQ) São Paulo.

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