Mechanistic investigations of the biginelli reaction using experimental and theoretical approaches

• Grant number: 17/02364-0
• Support Opportunities: Scholarships abroad - Research
• Start date: August 01, 2017
• End date: July 31, 2018
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Rodrigo Antonio Cormanich
• Grantee: Rodrigo Antonio Cormanich
• Host Investigator: Daniel Singleton
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Institution abroad: Texas A&M University, United States

Abstract

In this research project we propose the mechanistic study of the Biginelli reaction, using theoretical and experimental approaches. Classical experimental approaches for mechanism reaction studies will be applied as kinetic isotope effects (KIE), crossover experiments, isolation or trapping of intermediates and determination of rate laws. Theoretical calculations will also be applied in order to compare with and elucidate the experimental results. Theoretical calculations based on ab initio theoretical methods and also using several DFT functionals will be carried out. Molecular Dynamics (MD) calculations will be applied in order to look for all atomic motions that transform reactants to products, which are not possible to be probed by conventional computational studies. It is expected that these calculations, not previously applied over the Biginelli reaction, may help to enlighten the mechanism of this very important reaction which is being aim of many debates currently into the literature.

Scientific publications

(7)

(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)

ANDRADE, LAIZE A. F.; SILLA, JOSUE M.; CORMANICH, RODRIGO A.; FREITAS, MATHEUS P.. Infrared Fingerprints of n(N) -> sigma{*}(NH) Hyperconjugation in Hydrazides. Journal of Organic Chemistry, v. 82, n. 23, p. 12181-12187, DEC 1 2017. (17/02364-0)

RODRIGUES JR, MANOEL T.; SANTOS, HUGO; ZEOLY, LUCAS A.; SIMONI, DEBORAH A.; MOYANO, ALBERT; COELHO, FERNANDO. Preparation of tetrahydro-1H-xanthen-1-one and chromen-1-one derivatives via a Morita-Baylis-Hillman/oxa-Michael/elimination cascade. ARKIVOC, n. 2, p. 77+, 2020. (13/07600-3, 15/09205-0, 18/02611-0, 17/02364-0)

MARTINS, FRANCISCO A.; ZEOLY, LUCAS A.; CORMANICH, RODRIGO A.; FREITAS, MATHEUS P.. Solution conformations for the flexible 1-chloro-1,1-difluoro-2-pentanol unveiled using multinuclear magnetic resonance. Tetrahedron, v. 74, n. 8, p. 880-883, FEB 22 2018. (17/02364-0)

FERNANDES, FABIO DE SOUZA; CORMANICH, RODRIGO A.; ZEOLY, LUCAS A.; FORMIGA, ANDRE LUIZ B.; COELHO, FERNANDO. Employing Small Polyfunctionalized Molecules for a Diastereoselective Synthesis of Highly Substituted Indolines. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2018, n. 24, p. 3211-3223, JUN 29 2018. (17/02364-0, 13/07600-3)

RODRIGUES JR, MANOEL T.; SANTOS, HUGO; ZEOLY, LUCAS A.; SIMONI, DEBORAH A.; MOYANO, ALBERT; COELHO, FERNANDO. Preparation of tetrahydro-1H-xanthen-1-one and chromen-1-one derivatives via a Morita-Baylis-Hillman/oxa-Michael/elimination cascade. ARKIVOC, v. N/A, p. 60-pg., 2020-01-01. (17/02364-0, 13/07600-3, 18/02611-0, 15/09205-0)

MENDONCA, JOAO G. P.; FERNANDES, SERGIO A.; CORMANICH, RODRIGO A.; FREITAS, MATHEUS P.. Anion effect on the conformational equilibrium of sulfamide and its N,N-diindolyl derivative: Insights on anion transportation. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, v. 31, n. 9, SEP 2018. (17/02364-0)

ANDRADE, LAIZE A. F.; SILLA, JOSUE M.; CORMANICH, RODRIGO A.; FREITAS, MATHEUS P.. Infrared Fingerprints of n(N) -> sigma*(NH) Hyperconjugation in Hydrazides. Journal of Organic Chemistry, v. 82, n. 23, p. 7-pg., 2017-12-01. (17/02364-0)