A meta-selective C-H borylation and C-H olefination by noncovalent interactions: computational study

• Grant number: 22/01685-6
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• Start date: June 01, 2022
• End date: September 30, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Ataualpa Albert Carmo Braga
• Grantee: Daniel Arley Santos Oliveira
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Associated scholarship(s): 24/03646-3 - Reactivity and Aromaticity: a Kohn-Sham Molecular Orbital Perspective., BE.EP.DD

Abstract

The control of noncovalent interactions has been increasingly used to direct the regioselectivity of reactions involving unactivated arenes. Pd-Catalyzed meta-selective C-H olefination and Ir-Catalyzed C-H borylation has been highlighted in the specialized literature. Despite the growing interest in the description and control of noncovalent interactions in regioselectivity, there are few studies that make use of computational methodologies in detailing the interactions present and how ligands, solvents, substrates and even the metallic center could be specifically designed according to the products of interest. Therefore, the main objective of this research project is to carry out a detailed computational study, mainly using methods based on quantum mechanics, of the meta-selective C-H olefination/borylation reactions directed by noncovalent interactions. It is expected that, based on the results obtained, we will be able to suggest modifications in the reaction protocols, as in relation to the design of new ligands, as well as the participation of different substrates, solvents and transition metals. (AU)

Scientific publications

(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)

OLIVEIRA, DANIEL A. S.; BRAGA, ATAUALPA A. C.. Noncovalent Interactions in Palladium(II)-Catalyzed Meta-Selective C-H Functionalization: Mechanistic Insights and Origins of Regioselectivity. ChemPhysChem, v. N/A, p. 9-pg., 2024-11-05. (15/01491-3, 22/01685-6)

ALVES, ERICK H. S.; OLIVEIRA, DANIEL A. S.; BRAGA, ATAUALPA A. C.. Palladium(II)-catalyzed annulation of N-methoxy amides and arynes: computational mechanistic insights and substituents effects. Journal of Molecular Modeling, v. 30, n. 5, p. 11-pg., 2024-05-01. (15/01491-3, 22/01685-6, 22/16623-6)

CAETANO, RENAN B. G.; SANTIAGO, PEDRO H. O.; ELLENA, JAVIER A.; OLIVEIRA, DANIEL A. S.; BRAGA, ATAUALPA A. C.; LIMA-NETO, BENEDITO S.. Intriguing combinations of p-cymene, chloride ion, phosphines, and amines in ruthenium metal centers: Which ligand decoordinates for ROMP?. MOLECULAR CATALYSIS, v. 569, p. 12-pg., 2024-09-25. (23/17102-2, 17/15850-0, 22/01685-6, 21/10066-5, 15/01491-3)