Development of photochemical and electrocatalytic methodologies to the synthesis and modification of heterocyclic scaffolds

• Grant number: 18/12986-1
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Start date: September 01, 2018
• End date: March 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Agreement: GlaxoSmithKline
• Principal Investigator: Márcio Weber Paixão
• Grantee: Camila de Menezes Kisukuri
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil
• Associated research grant: 14/50249-8 - Green chemistry: sustainable synthetic methods employing benign solvents, safer reagents, and bio-renewable feedstock, AP.PCPE

Abstract

The chemical and industry development has made it possible to make changes in feedstock as well the creation of new materials, which can lead to facilitate the modernization of the society's lifestyle. However, progress has been accompanied by increased use of non-renewable sources and waste generation, drawing attention to environmental issues. Thus, the concept of green chemistry emerges to improve this request and, in this context, photo- and electrocatalytic approaches are gaining prominent positions as mediators of radical reactions.These approaches have some advantages when compared to traditional systems - Perhaps, the largest of them is the replacement of oxidizing and reducing reagents (most of them show high toxicity, difficult transportation and storage, and lead to a large waste generation) by the use of an electron current. In addition, this alternative synthesis methodology allows in situ generation of unstable reagents, by working in safe conditions and controlling the oxidation/reduction potential, thus allowing the development of highly selective processes.Therefore, this project aims to explore photochemical reactions promoted by visible light through photoredox catalysis mediated by transition metals and photo-organocatalysts.After, we intend to develop electrochemical and photoelectrocatalytic processes in batch or continuous flow for the synthesis and functionalization of heterocyclic systems. In this context, the stereoselective synthesis of nitrogenous systems will be evaluated through the combination of an electrochemical oxidation and an organocatalysed reaction. In addition, this proposal presents other perspectives, especially in the generation of radical species through the electrooxidation of carboxylic compounds, with subsequent scrambling, aiming at the synthesis of heterocyclic systems. To this end, nanostructured electrodes materials should be properly synthesized and characterized.

Scientific publications

(6)

(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)

KISUKURI, CAMILA M.; FERNANDES, VITOR A.; DELGADO, JOSE A. C.; HAERING, ANDREAS P.; PAIXAO, MARCIO W.; WALDVOGEL, SIEGFRIED R.. Electrochemical Installation of CFH2-, CF2H-, CF3-, and Perfluoroalkyl Groups into Small Organic Molecules. CHEMICAL RECORD, JUN 2021. (19/01973-9, 18/12986-1, 15/17141-1, 14/50249-8)

KISUKURI, CAMILA M.; FERNANDES, VITOR A.; DELGADO, JOSE A. C.; HAERING, ANDREAS P.; PAIXAO, MARCIO W.; WALDVOGEL, SIEGFRIED R.. Electrochemical Installation of CFH2-, CF2H-, CF3-, and Perfluoroalkyl Groups into Small Organic Molecules. CHEMICAL RECORD, v. 21, n. 9, SI, p. 2502-2525, SEP 2021. (18/12986-1, 15/17141-1, 14/50249-8, 19/01973-9)

MATSUO, BIANCA T.; CORREIA, JOSE TIAGO M.; PAIXAO, MARCIO W.. Visible-Light-Mediated alpha-Amino Alkylation of Azomethine Imines: An Approach to N-(beta-Aminoalkyl)pyrazolidinones. ORGANIC LETTERS, v. 22, n. 20, p. 7891-7896, OCT 16 2020. (14/50249-8, 15/17141-1, 18/12986-1, 17/10015-6)

CORREIA, JOSE TIAGO M.; DA SILVA, GUSTAVO PIVA; KISUKURI, CAMILA M.; ANDRE, ELIAS; PIRES, BRUNO; CARNEIRO, PABLO S.; PAIXAO, MARCIO W.. Metal-Free Photoinduced Hydroalkylation Cascade Enabled by an Electron-Donor-Acceptor Complex. Journal of Organic Chemistry, v. 85, n. 15, p. 9820-9834, AUG 7 2020. (14/50249-8, 15/17141-1, 18/12986-1, 17/10015-6)

MALLAUPOMA, LENNA ROSANIE CORDERO; DIAS, BARBARA KARINA DE MENEZES; SINGH, MANEESH KUMAR; HONORIO, RUTE ISABEL; NAKABASHI, MYNA; KISUKURI, CAMILA DE MENEZES; PAIXAO, MARCIO WEBER; GARCIA, CELIA R. S.. Decoding the Role of Melatonin Structure on Plasmodium falciparum Human Malaria Parasites Synchronization Using 2-Sulfenylindoles Derivatives. BIOMOLECULES, v. 12, n. 5, p. 15-pg., 2022-05-01. (18/12986-1, 17/08684-7, 19/09490-7)

PAIXAO, MARCIO W.. Photoredox Catalysis toward 2-Sulfenylindole Synthesis through a Radical Cascade Process. ORGANIC LETTERS, v. 22, n. 11, p. 4266-4271, JUN 5 2020. (14/50249-8, 17/03120-8, 18/12986-1, 15/17141-1)