Development of substrate controlled asymmetric Suzuki-Miyaura biaryl couplings using chiral N,N-ligands and synthetic potential applications

• Grant number: 17/10931-2
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor
• Start date: September 01, 2017
• End date: August 31, 2018
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Shivashankar Kattela
• Supervisor: José M. Lassaletta
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Institution abroad: Instituto de Investigaciones Químicas (IIQ), Spain
• Associated to the scholarship: 14/05407-4 - Strategies for the dessymmetrization of cyclopentene scaffolds using the enantioselective Heck-Matsuda reaction and their potential synthetic applications., BP.PD

Abstract

Among Pd-catalyzed cross-coupling reactions, Suzuki-couplings play an important role in organic chemistry. Construction of the configurationally stable biaryl system is a challenging task due to low rotational barrier, they easily undergo torsional isomerization around aryl-aryl bond. Chiral biaryl motifs are important structural elements in asymmetric synthesis and are present in many pharmaceutical agents and natural products. The aim at this proposal: For the past several years our group has been focused on the development of substrate directed enantioselective Heck-Matsuda reactions. Encourag by these results, and new ones, we wish to further to explore the viability of this directing group approach towards the Suzuki-Miyaura biaryl couplings in an enantioselective fashion. Preliminary results have demonstrated the involvement of Correia-Pfaltz ligand (Scheme 1) and directing group (-CHO) in the Suzuki-Miyaura biaryl coupling. We believe this directing group (DG) concept using our group invented new N,N-bidentate ligands constitutes an opportunity to investigate the Suzuki-Miyaura couplings. Next, using computational studies we wish to evaluate the mechanism of the Suzuki-Miyaura reaction and to identify the favored transition state, the origin of stereoselectivity and the role of the directing group in the reactions. Finally, we wish to apply this methodology for the total synthesis of antimalarial Dioncopeltine A and synthesis of Biaryl ligands its application in asymmetric catalysis. Due to the importance of biaryl systems, our promising preliminary results associated with a still incipient understanding of the role of N, N-bidentate ligands in the enantioselective synthesis of these frameworks, we believe that the further investigation of the reactions is highly desirable. (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)

KATTELA, SHIVASHANKAR; CORREIA, CARLOS ROQUE D.; ROS, ABEL; HORNILLOS, VALENTIN; IGLESIAS-SIGU, JAVIER; FERNANDEZ, ROSARIO; LASSALETTA, JOSE M.. Pd-Catalyzed Dynamic Kinetic Asymmetric Cross-Coupling of Heterobiaryl Bromides with N-Tosylhydrazones. ORGANIC LETTERS, v. 24, n. 21, p. 5-pg., 2022-06-03. (17/10931-2)