New Approaches in Enantioselective Heck-Matsuda Reactions via Tandem Catalysis

• Grant number: 24/20078-9
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Start date: May 01, 2025
• End date: April 30, 2028
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Gustavo Henrique Cicero Masson
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant: 23/00383-9 - Self-sustaining enantioselective Heck-Matsuda reactions via diazonium salts generated in situ from anilines or nitroarenes in in-tandem or one-pot cascade strategies, AP.R

Abstract

This project will aim to develop new enantioselective methodologies for C-C coupling, using the Heck-Matsuda (HM), Stille, and Negishi reactions, as well as the carbonylative Heck-Matsuda. The central proposal will involve the use of diazonium salts, which will offer advantages over conventional precursors such as aryl halides. The research will evaluate different stannanes in the Stille reactions and organozincs in the Negishi reactions during the transmetallation process, in order to optimize the conditions for coupling with enantioselective Heck reactions. This approach will allow for a greater diversity of functionalizations, essential for modern organic chemistry. Additionally, the carbonylative Heck-Matsuda methodology will be employed to further expand the options for functionalization in cross-couplings. An innovative aspect of the project will be the implementation of the coupling between diazotization/Heck-Matsuda carbonylative/Stille (or Negishi), avoiding the need to use isolated diazonium salts, which will be generated in-situ. This will require careful investigation of the reaction conditions to ensure that there is no interference with other mechanisms occurring simultaneously in a tandem process in the presence of chiral N,N-ligands. This proposed approach will also expand the scope of chemical transformations, contributing to the development of new synthetic methodologies that can be applied in various areas of organic chemistry and in the synthesis of complex enantioenriched compounds.