Evaluating new palladium chiral catalysts and application in enantioselective Heck-Matsuda reaction development in new olefinic models: computational studies

• Grant number: 17/18207-1
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Effective date (Start): October 01, 2017
• Effective date (End): December 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Vitor Hugo Menezes da Silva
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes, AP.TEM

Abstract

Palladium-catalyzed cross-coupling reactions constitute an extremely useful and powerful class of reactions available for organic synthesis nowadays. Among these reactions involving aryl halides/tosylates/mesylates as one of the partner reagents, we could mention the following couplings: i) the Heck-Mizoroki reactions, with olefins, ii) the Negishi coupling, employing organozinc and organoaluminum reagents, iii) the Corriu-Kumada-Murashashi coupling, with Grignard reagents, iv) the Stille coupling, involving organostannes, v) the Suzuki-Miyaura coupling of organoboranes, vi) the Hiyama coupling, using organosilicon compounds, and vii) the Sonogashira coupling of terminal alkynes. Despite the reasonably large number of those coupling reactions, there is still plenty of chemical room for further development and applications of those processes in view of their broad scope. Several key features of these processes are still unclear or were not investigated in depth at all. Moreover, many of those reactions need more work to achieve a higher level of applicability in synthesis. Aiming at getting on the frontline of knowledge of these coupling reactions, we are proposing as goals of the present project, i) a deeper understanding of the mechanistic aspects of these processes promoted by Pd, in particular of those involving the Heck arylations using arenediazonium tetrafluoroborates (the Heck-Matsuda arylations), ii) a mild migration from homogeneous conditions of these coupling reactions to heterogeneous conditions, which prove themselves applicable to continuous flow, and iii) the development and application of less well-known couplings, with emphasis on C-H oxidative activation, such as the Fujiwara-Moritani reactions and the Tsutsui-Narasaka reactions to synthesize heterocyclic compounds. The project encompasses all three aspects mentioned above, posing as specific goals: 1) to expand the use of the cross-coupling methods catalyzed by palladium at the same time it investigates new frontiers, such as the chirality transfer in the Heck-Matsuda reactions (enantioselective Heck-Matsuda reactions employing arenediazonium salts) in batch as well as using reactions in flow, 2) new applications for the oxidative cross-couplings of aromatic systems, 3) the use of palladium for the construction of new functional organic materials, 4) the application of modern computational methods to study and elucidate the precise mechanism of these reactions catalyzed by palladium, 5) to evaluate the inhibition of the proteasome and other enzymatic targets aiming at neglected diseases and, 6) the development and application of new dyes for sensitized solar cells.

Scientific publications

(6)

(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 OLIVEIRA, JULIANA MANSO; ANGNES, RICARDO ALMIR; KHAN, ISMAT ULLAH; POLO, ELLEN CHRISTINE; HEERDT, GABRIEL; SERVILHA, BRUNO M.; MENEZES DA SILVA, VITOR H.; BRAGA, ATAUALPA A. C.; DUARTE CORREIA, CARLOS ROQUE. Enantioselective, Noncovalent, Substrate-Directable Heck-Matsuda and Oxidative Heck Arylations of Unactivated Five-Membered Carbocyclic Olefins. CHEMISTRY-A EUROPEAN JOURNAL, v. 24, n. 45, p. 11738-11747, AUG 9 2018. (17/18207-1, 13/00544-0, 14/25770-6, 13/07600-3, 15/01491-3, 16/04963-6, 13/25849-9)

DUARTE CHORRO, TOMAZ HENRIQUE; SCARPA DE SOUZA, EDSON LEONARDO; KOSTER, OTTO DAOLIO; POLO, ELLEN CHRISTINE; CARMONA, RAFAELA COSTA; MENEZES DA SILVA, VITOR HUGO; BATISTA JUNIOR, JOAO MARCOS; DUARTE CORREIA, CARLOS ROQUE. In Tandem Enantioselective Intramolecular Heck-Matsuda Reactions directly from Anilines. ADVANCED SYNTHESIS & CATALYSIS, v. 365, n. 2, p. 13-pg., 2023-01-11. (13/07600-3, 18/16916-8, 19/25657-9, 19/22319-5, 14/25770-6, 18/00271-8, 17/18207-1, 18/02945-6)

MENEZES DA SILVA, VITOR H.; MORGON, NELSON H.; CORREIA, CARLOS R. D.; BRAGA, ATAUALPA A. C.. DFT perspective on the selectivity and mechanism of ligand-free Heck reaction involving allylic esters and arenediazonium salts. JOURNAL OF ORGANOMETALLIC CHEMISTRY, v. 896, p. 5-15, SEP 15 2019. (11/07895-8, 17/18207-1, 14/25770-6, 15/01491-3, 13/04813-6)

MENEZES DA SILVA, VITOR H.; OLIVEIRA, CAIO C.; CORREIA, CARLOS ROQUE D.; BRAGA, ATAUALPA A. C.. Heck arylation of acyclic olefins employing arenediazonium salts and chiral N,N ligands: new mechanistic insights from quantum-chemical calculations. THEORETICAL CHEMISTRY ACCOUNTS, v. 139, n. 4, APR 4 2020. (15/01491-3, 17/18207-1, 14/25770-6)

DE OLIVEIRA, VALDEIR C.; DE OLIVEIRA, JULIANA M.; MENEZES DA SILVA, VITOR H.; KHAN, ISMAT U.; CORREIA, CARLOS ROQUE D.. Enantioselective Heck-Matsuda Reactions of Spirocyclopentenyl Hydantoins Directed by Non-Covalent Interactions: Total Synthesis of the (S,S)-VPC01091. ADVANCED SYNTHESIS & CATALYSIS, v. 362, n. 16, JUL 2020. (13/07600-3, 14/25770-6, 17/18207-1, 15/01491-3)

WIETHAN, CARSON; BRAGA, INGREDY B.; MENEZES DA SILVA, VITOR H.; BATISTA JR, JOAO M.; CORREIA, CARLOS ROQUE D.. Enantioselective Synthesis of Isoindolones via Palladium - Catalyzed Intramolecular Heck-Mizoroki Reactions of Endocyclic Enamides Using N,N-Ligands. CHEMCATCHEM, v. N/A, p. 7-pg., 2023-05-31. (13/07600-3, 19/22319-5, 17/18207-1, 18/08627-6, 14/25770-6)