Theoretical study on selectivity in Heck-Mizoroki reactions: comparisons between nickel and palladium catalytic systems

• Grant number: 15/11840-5
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• Effective date (Start): October 06, 2015
• Effective date (End): October 05, 2016
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Ataualpa Albert Carmo Braga
• Grantee: Vitor Hugo Menezes da Silva
• Supervisor: Thomas R. Cundari
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Research place: University of North Texas, United States
• Associated to the scholarship: 13/04813-6 - Mechanistic studies of Heck-Matsuda reactions: a theoretical investigation, BP.DR

Abstract

Palladium-catalyzed C-C cross-coupling reactions are among the most important fields in organic synthesis and organometallic chemistry. The Nobel Prize in Chemistry 2010 was awarded to its main developers, Richard Heck, Ei-Ichi Negishi e Akira Suzuki, reflecting the importance of these reactions in modern chemical sciences.A complete characterization of the mechanism of Palladium-catalyzed C-C cross-coupling reactions, using purely experimental methods, is still challenging. At this point, computational chemistry has proven essential for elucidating the mechanism and shaping our current understandingof the catalytic cycles. Computational investigations provides an opportunity to further expand these reactions to new substrates and catalysis. The PhD research project of the candidate propose a theoretical investigation of the Heck-Matsuda reaction,that uses arenediazonium salts as an alternative electrophiles to aryl halide, often used in the Heck-Mizoroki reactions. Herein, we proposed an expansion of the original project, by use of nickel (Ni) catalyst in Heck-Mizoroki reactions.The main aim of this project is elucidate the origin of the selectivity in severals Heck-Mizorokireactions based in both nickel and palladium catalytic systems, mostly using Density Functional Theory (DFT). In addition, we intend to improve the theoretical model for large systems (>100 atoms) performing QM/MM calculations based on ONIOM method. (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)

MENEZES DA SILVA, VITOR H.; MONEZI, NATALIA M.; ANDO, ROMULO A.; BRAGA, ATAUALPA A. C.. New insights into the electrophilic aromatic substitution mechanism of tricyanovinylation reaction involving tetracyanoethylene and N,N-dimethylaniline: An interpretation based on density functional theory calculations. Journal of Molecular Structure, v. 1142, p. 58-65, AUG 15 2017. (15/01491-3, 15/11840-5, 13/04813-6, 14/25770-6)

MENEZES DA SIVA, VITOR H.; BRAGA, ATAUALPA A. C.; CUNDARI, THOMAS R.. N-Heterocyclic Carbene Based Nickel and Palladium Complexes: A DFT Comparison of the Mizoroki-Heck Catalytic Cycles. Organometallics, v. 35, n. 18, p. 3170-3181, SEP 26 2016. (13/04813-6, 15/11840-5, 15/01491-3)

ANSELL, MELVYN B.; DA SILVA, VITOR H. MENEZES; HEERDT, GABRIEL; BRAGA, ATAUALPA A. C.; SPENCER, JOHN; NAVARRO, OSCAR. An experimental and theoretical study into the facile, homogenous (N-heterocyclic carbene)(2)-Pd(0) catalyzed diboration of internal and terminal alkynes. CATALYSIS SCIENCE & TECHNOLOGY, v. 6, n. 20, p. 7461-7467, 2016. (13/04813-6, 15/11840-5, 15/01491-3)

VASCONCELOS, STANLEY N. S.; MENEZES DA SILVA, VITOR H.; BRAGA, ATAUALPA A. C.; SHAMIM, ANWAR; SOUZA, FREDERICO B.; PIMENTA, DANIEL C.; STEFANI, HELIO A.. 3-Alkenyltyrosines Accessed by Suzuki-Miyaura Coupling: A Key Intermediate in the Synthesis and Mechanistic Study of Povarov Multicomponent Reactions. ASIAN JOURNAL OF ORGANIC CHEMISTRY, v. 6, n. 7, p. 913-920, JUL 2017. (13/17960-7, 12/00424-2, 15/01491-3, 13/04813-6, 15/11840-5)