Chasing sustainability: photoinduced synthesis of dicarboxylic systems from alkenes via CO2 or a CO2/carbamoyl-radical cocktail

• Grant number: 23/05334-6
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• Start date: July 01, 2023
• End date: June 30, 2024
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Márcio Weber Paixão
• Grantee: Kimberly Benedetti Vega
• Supervisor: Burkhard Koenig
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil
• Institution abroad: University of Regensburg, Germany
• Associated to the scholarship: 21/01354-7 - Photocatalysis applied to difunctionalization of alkenes via CO2 incorporation: multicomponent synthesis of ²-sulfonil and ±- (2-sulfenyl-indolyl) -carboxylic acids, BP.DR

Abstract

Carboxylic acids and their derivatives are prominent chemical motifs with vast applications in both industry and academy. Amidst various ways of synthesizing carboxylic acids, the incorporations of CO2 into organic molecules is considered one of the most compelling and environmentally friendly strategy. In recent years, photocatalytic CO2 fixation for the monoacids synthesis has been a hot topic of research. However, the process of dicarboxylation - which involves the simultaneous incorporation of two carboxyl units using CO2 as the sole source or a combination of CO2 and carbamoyl radical - remains relatively less explored. In this context, this proposal aims to fulfil the gaps of prior contributions on the 1,2-dicarboxylation of alkenes through two distinct scenarios: i) Develop a metal-free, redox-neutral and regioselective method for the simple and straightforward synthesis of succinamic acids using styrenes, carbamoyl radicals and carbon dioxide as carboxylation agent. ii) Synthesize maleic/fumaric acids from succinic acids through the double addition of CO2 - which will be generated through a Consecutive Photoinduced Electron Transfer (ConPET) - in olefins with low reduction potential (d -2.21 V). (AU)