Self-sustaining enantioselective Heck-Matsuda reactions via diazonium salts generated in situ from anilines or nitroarenes in in-tandem or one-pot cascade strategies

• Grant number: 23/00383-9
• Support Opportunities: Regular Research Grants
• Start date: June 01, 2023
• End date: May 31, 2025
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Carlos Roque Duarte Correia
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated scholarship(s): 24/20078-9 - New Approaches in Enantioselective Heck-Matsuda Reactions via Tandem Catalysis, BP.PD; 24/01003-8 - Development of new chiral N,N ligands and their applications in self-sustained enantioselective Heck-Matsuda reactions via diazonium salts generated in situ from anilines or nitroarenes, BP.TT

Abstract

The research project aims to develop new sequentially enantioselective intermolecular and intramolecular enantioselective Heck arylation reactions of non-activated olefins, with the in-situ generation of arenediazonium salts directly from substituted anilines and/or nitroarenes. The reactions will be carried out in cascade, without isolating the products generated during an in-tandem or "one-pot cascade" process. Starting from the reduction of nitroarenes, the anilines generated in the medium will undergo a diazotization reaction with organic nitrites, producing the respective diazonium salts, which in the presence of olefins will undergo enantioselective Heck-Matsuda reactions promoted by chiral N,N ligands present in the reaction medium. Sequential reactions will be carried out intermolecularly and intramolecularly, extending the challenge to the synthesis of complex compounds with potential application in the construction of bioactive compounds.Aiming at greater practicality, the sequential reactions will involve olefin desymmetrization processes. The intramolecular version will also involve eliminative and carbonylative Heck arylation reactions, with the expectation of building benzoxacinic and spiro systems, including quaternary centers. Variations both in the aromatic ring and in the olefinic part should provide an expressive number of highly complex products in an enantioselective way.Among the expected benefits of this project, there are: (i) Formation of diastereo- and enantioenriched building blocks with high added value, whose structures can be found in several natural products with biological activity, (ii) Development of practical, sequential methods, effective and self-sustaining that demonstrate the generality and robustness of Heck Matsuda's enantioselective cascade reactions, (iii) The study of cascade reactions will bring important contributions not only to the research group but also to the field of organometallic chemistry and catalysis as a whole.The objective is also to test these new organic compounds for their pharmacological potential since this project is associated with the Center for Research, Innovation, and Dissemination (CEPID/CIBFar), Center for Innovation in Biodiversity and Pharmaceuticals (Fapesp 2013/07600-3), coordinated by Prof. Glaucius Oliva, aiming to explore bioactive compounds against diseases such as malaria, cancer, Chagas disease and the discovery of new compounds with antibacterial activity. (AU)

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)

DE SOUZA, EDSON LEONARDO SCARPA; NEUMANN, HELFRIED; CORREIA, CARLOS ROQUE DUARTE; BELLER, MATTHIAS. Proposing Oxalic Acid as Chemical Storage of Carbon Dioxide to Achieve Carbon Neutrality. CHEMSUSCHEM, v. 18, n. 3, p. 7-pg., 2024-12-04. (22/14575-4, 14/25770-6, 19/25657-9, 23/00383-9)

DIOGENIS, ISABELA MOREIRA SOARES; BISPO-JR, AIRTON GERMANO; PIROVANI, RODRIGO VEZULA; SARAIVA, LEONARDO FIGUEIREDO; GOZZO, FABIO CESAR; CORREIA, CARLOS ROQUE DUARTE; MAZALI, ITALO ODONE; NOME, RENE ALFONSO; SIGOLI, FERNANDO APARECIDO. Towards opto-structural parameters to enhance the circularly polarized luminescence brightness of Eu^III β-diketone complexes with chiral auxiliary ligands. JOURNAL OF MATERIALS CHEMISTRY C, v. 12, n. 14, p. 11-pg., 2024-03-11. (14/25770-6, 20/02614-0, 21/06326-1, 14/50906-9, 23/00383-9)

CHORRO, TOMAZ HENRIQUE DUARTE; KAUSSLER, CLEMENS; KOLODIAZHNAIA, JULIA V.; JENSEN, FRANK; SKRYDSTRUP, TROELS; CORREIA, CARLOS ROQUE D.. Tandem synthesis of enantioenriched spirolactones via one-pot Heck-Matsuda reactions directly from nitroarenes. ORGANIC CHEMISTRY FRONTIERS, v. 12, n. 4, p. 9-pg., 2024-12-17. (13/07600-3, 14/25770-6, 21/14298-8, 23/00383-9, 22/07887-0)

COELHO, SERGIO FERNANDO NUNES; BISPO-JR, AIRTON GERMANO; DE OLIVEIRA, NAGYLA ALVES; MAZALI, ITALO ODONE; SIGOLI, FERNANDO APARECIDO. Eu^III and Tb^III upconversion intermediated by interparticle energy transfer in functionalized NaLnF₄ nanoparticles. NANOSCALE, v. 16, n. 15, p. 11-pg., 2024-03-05. (14/25770-6, 20/02614-0, 21/06326-1, 14/50906-9, 21/08111-2, 23/00383-9)