Exploiting Photocatalyzed Reactions Under Continuous Flow Conditions by using Porphyrinoid Systems: (C-FlowPhotoChem)

• Grant number: 15/21110-4
• Support Opportunities: Regular Research Grants
• Start date: March 01, 2016
• End date: February 28, 2018
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Kleber Thiago de Oliveira
• Grantee: Kleber Thiago de Oliveira
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil
• City of the host institution: São Carlos

Abstract

In this project, continuous flow photocatalyzed reactions will be exploited by using porphyrinoid systems as photocatalysts (Figure i). The main objective here is to advance on the promotion and scalability of photocatalyzed process in which already presented some limitations to be performed. In addition, we intend to exploit the huge photocatalytic potential which porphyrins may represent for preparative photocatalyzed reactions (scale-up). Thus, we have selected two relevant reactions which present some technical limitations on the execution in organic synthesis: endoperoxidations/Kornblum-DeLaMare rearrangements and oxidative cyclizations of tertiary amines by using photocatalysis - Double C-H functionalization. In the first part of the project we intend to study the best condition for the endoperoxidation reactions by testing a scope of dienes, all of them under continuous flow generation. Thus, we intend to study the in-line Kornblum-DeLaMare rearrangement aiming at for security, scaling-up of the process as well as the further preparation of phosphorylated inositol and polihydroxylated enzymatic inhibitors. In the second part of this project we intend to evaluate the potential of some porphyrin derivatives for use in SET (single electron transfer) photocatalytic reactions by the generation of tertiary amine radical cations and further reaction with electrophiles aiming at the synthesis of tetrahydroquinoline systems under continuous flow conditions. (AU)

Scientific publications

(17)

(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)

LINARES, IRWIN A. P.; DE OLIVEIRA, KLEBER T.; PERUSSI, JANICE RODRIGUES. Chlorin derivatives sterically-prevented from self-aggregation with high antitumor activity for photodynamic therapy. DYES AND PIGMENTS, v. 145, p. 518-527, OCT 2017. (13/07276-1, 15/21110-4)

DONATONI, MARIA C.; VIEIRA, YGOR W.; BROCKSOM, TIMOTHY J.; RABELO, ADRIANO C.; LEITE, EDSON R.; DE OLIVEIRA, KLEBER T.. One-pot sequential functionalizations of meso-tetrathienylporphyrins via Heck-Mizoroki cross-coupling reactions. Tetrahedron Letters, v. 57, n. 27-28, p. 3016-3020, JUL 6 2016. (11/13993-2, 13/07276-1, 15/21110-4, 13/06532-4)

PAVANI, CHRISTIANE; FRANCISCO, CLAUDIA M. L.; GOBO, NICHOLAS R. S.; DE OLIVEIRA, KLEBER T.; BAPTISTA, MAURICIO S.. Improved photodynamic activity of a dual phthalocyanine-ALA photosensitiser. NEW JOURNAL OF CHEMISTRY, v. 40, n. 11, p. 9666-9671, 2016. (15/21110-4, 13/07276-1, 12/50680-5, 12/24092-9, 13/07937-8, 09/01524-8)

LEITE, TAISE H. O.; GRAWE, GREGORY; HONORATO, JOAO; CUNHA, BEATRIZ N.; NASCIMENTO, OTACIRO R.; DE VARGAS, PAMELA S.; DONATONI, CAROLINA; OLIYEIRA, KLEBER T.; LOPES, JEFFERSON M. S.; BARBOSA NETO, NEWTON M.; et al. Remarkable Electronic Effect on the meso-Tetra(thienyl)porphyrins. Inorganic Chemistry, v. 58, n. 2, p. 1030-1039, JAN 21 2019. (18/00106-7, 15/21110-4, 16/16312-0)

BARONA-CASTANO, JUAN C.; CARMONA-VARGAS, CHRISTIAN C.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Porphyrins as Catalysts in Scalable Organic Reactions. Molecules, v. 21, n. 3, MAR 2016. (11/13993-2, 13/07276-1, 15/21110-4)

DE SOUZA, JULIANA M.; BROCKSOM, TIMOTHY J.; MCQUADE, D. TYLER; DE OLIVEIRA, KLEBER T.. Continuous Endoperoxidation of Conjugated Dienes and Subsequent Rearrangements Leading to C-H Oxidized Synthons. Journal of Organic Chemistry, v. 83, n. 15, p. 7574-7585, AUG 3 2018. (11/13993-2, 13/07276-1, 18/00106-7, 15/21110-4)

DIOGO, PATRCIA; FERNANDES, CHANTAL; CARAMELO, FRANCISCO; MOTA, MARTA; MIRANDA, ISABEL M.; FAUSTINO, M. A. F.; NEVES, M. G. P. M. S.; ULIANA, MARCIANA P.; DE OLIVEIRA, KLEBER T.; SANTOS, JOAO M.; et al. Antimicrobial Photodynamic Therapy against Endodontic Enterococcus faecalis and Candida albicans Mono and Mixed Biofilms in the Presence of Photosensitizers: A Comparative Study with Classical Endodontic Irrigants. FRONTIERS IN MICROBIOLOGY, v. 8, MAR 30 2017. (13/07276-1, 15/21110-4)

MORITZ, MILENE N. O.; GONCALVES, JOYCE L. S.; LINARES, IRWIN A. P.; PERUSSI, JANICE R.; DE OLIVEIRA, KLEBER T.. Semi-synthesis and PDT activities of a new amphiphilic chlorin derivative. Photodiagnosis and Photodynamic Therapy, v. 17, p. 39-47, MAR 2017. (15/21110-4, 13/07276-1)

MUELLER, ANDRESSA V.; RAMOS, LUIZ D.; FRIN, KARINA P. M.; DE OLIVEIRA, KLEBER T.; POLO, ANDRE S.. A high efficiency ruthenium(II) tris-heteroleptic dye containing 4,7-dicarbazole-1,10-phenanthroline for nanocrystalline solar cells. RSC ADVANCES, v. 6, n. 52, p. 46487-46494, 2016. (15/00605-5, 15/13149-8, 13/25173-5, 15/21110-4)

BARTOLOMEU, ALOISIO DE A.; BROCKSOM, TIMOTHY J.; DA SILVA FILHO, LUIZ C.; DE OLIVEIRA, KLEBER T.. Multicomponent reactions mediated by NbCl5 for the synthesis of phthalonitrile-quinoline dyads: Methodology, scope, mechanistic insights and applications in phthalocyanine synthesis. DYES AND PIGMENTS, v. 151, p. 391-402, APR 2018. (14/24506-3, 11/13993-2, 13/07276-1, 15/21110-4)

CARMONA-VARGAS, CHRISTIAN C.; ALVES, LEANDRO DE C.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Combining batch and continuous flow setups in the end-to-end synthesis of naturally occurring curcuminoids. REACTION CHEMISTRY & ENGINEERING, v. 2, n. 3, p. 366-374, JUN 2017. (11/13993-2, 13/07276-1, 15/21110-4, 15/11801-0)

MORITZ, MILENE N. O.; ROSSA JUNIOR, CARLOS; DE OLIVEIRA, KLEBER T.; ULIANA, MARCIANA P.; PERUSSI, JANICE R.. Phototoxicity in a laryngeal cancer cell line enhanced by a targeting amphiphilic chlorin photosensitizer. Photodiagnosis and Photodynamic Therapy, v. 19, p. 355-362, SEP 2017. (15/21110-4, 13/07276-1)

RAMOS, L. D.; SAMPAIO, R. N.; DE ASSIS, F. F.; DE OLIVEIRA, K. T.; HOMEM-DE-MELLO, P.; PATROCINIO, A. O. T.; FRIN, K. P. M.. Contrasting photophysical properties of rhenium(I) tricarbonyl complexes having carbazole groups attached to the polypyridine ligand. DALTON TRANSACTIONS, v. 45, n. 29, p. 11688-11698, 2016. (15/21110-4, 11/23408-0, 12/24096-4, 13/06532-4, 15/13149-8)

DE ANNUNZIO, SARAH RAQUEL; DE FREITAS, LAURA MARISE; BLANCO, ANA LIGIA; DA COSTA, MARDOQUEU MARTINS; CARMONA-VARGAS, CHRISTIAN C.; DE OLIVEIRA, KLEBER THIAGO; FONTANA, CARLA RAQUEL. Susceptibility of Enterococcus faecalis and Propionibacterium acnes to antimicrobial photodynamic therapy. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY, v. 178, p. 545-550, JAN 2018. (16/05345-4, 14/24581-5, 15/21110-4)

DE SOUZA, ALINE A. N.; SILVA, NATHALIA S.; MUELLER, ANDRESSA V.; POLO, ANDRE S.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Porphyrins as Photoredox Catalysts in Csp(2)-H Arylations: Batch and Continuous Flow Approaches. Journal of Organic Chemistry, v. 83, n. 24, p. 15077-15086, DEC 21 2018. (15/21110-4, 13/07276-1, 18/00106-7, 16/24020-9, 16/21993-6)

TIMOTHY J. BROCKSOM; KLEBER T. DE OLIVEIRA; ANDRÉ L. DESIDERÁ. The Chemistry of the Sesquiterpene Alkaloids. Journal of the Brazilian Chemical Society, v. 28, n. 6, p. 933-942, 2017-06-00. (15/21110-4, 11/13993-2)

GOBO, NICHOLAS R. S.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Soluble and Non-Aggregated Phthalocyanines: Synthesis, Mechanistic Aspects and Their Main Building Blocks. CURRENT ORGANIC SYNTHESIS, v. 14, n. 8, p. 1132-1155, 2017. (11/13993-2, 12/24092-9, 13/07276-1, 15/21110-4)