Photoinduced Synthesis of Selenides via Iron-Catalyzed Decarboxylation Reactions Mediated by Ligand-to-Metal Charge Transfer

• Grant number: 25/01367-2
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• Start date: May 01, 2025
• End date: April 30, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Ricardo Samuel Schwab
• Grantee: Thiago Rodrigues da Silva
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil

Abstract

The need for new technologies to optimize and develop novel reactions through green and efficient approaches is one of the major contemporary challenges in sustainable chemistry. Methodologies involving the use of Fe salts, which act both as the light-absorbing center and as a sustainable terminal oxidant, have reached a unique range of applicability compared to other metals, leading to the formation of radical species from carboxylic acids. The use of iron carboxylates, generated in situ from the reaction of iron salts with the respective carboxylic acids, in photoinduced decarboxylative coupling reactions avoids the pre-installation of redox-active organic groups as internal oxidants. In this context, although decarboxylative coupling reactions have already been applied in the synthesis of selenides from carboxylic acid derivatives containing a photoactive redox group, the use of free carboxylic acids as radical precursors in LMCT (Ligand-to-Metal Charge Transfer) processes has not yet been reported. The general objectives of this work are to explore LMCT chemistry in decarboxylative coupling reactions for the synthesis of selenides. This methodology will expand the synthetic potential involved in the synthesis of alkyl selenides catalyzed by Fe/visible light using free carboxylic acids, offering a powerful synthetic photochemical alternative that is currently focused on the use of non-commercial alkyl radical transfer reagents. The results obtained aim to directly impact the quality of the scientific production of the undergraduate research students and other researchers involved and contribute to the training of human resources at the undergraduate level. It is important to highlight that FAPESP supports this project under grant number 2021/12394-0. (AU)