Developing a Selective Cross Rauhut-Currier Reaction Through Mechanistic Investigations

• Applicant: Dr. Christina Wartmann
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 537721875

The overall objective of this project is the development of a highly selective method for cross Rauhut-Currier (RC) reactions, both inter- and intramolecular, of chemically similar Michael acceptors, with the additional goal of controlling which product is formed through the reaction conditions. Instead of an empirical screening of reaction conditions, a rational approach based on mechanistic studies is proposed. First, the reaction mechanism of the RC reaction will be elucidated through extensive experimental studies. A simple, selective cross RC reaction, such as the phosphine-catalysed coupling of ethyl acrylate and diethyl fumarate will be investigated first, as the analysis of this reaction is expected to be easier. Afterwards, a non-selective cross RC reaction, such as the reaction of ethyl acrylate and acrylonitrile, will be investigated. Although this reaction might be more challenging to analyse, side products and the observed product ratios will give additional information about the reaction mechanism. This information will be crucial for determining the selectivity determining step. With a preliminary mechanistic model in hand, the reaction conditions will be varied systematically to establish detailed correlations between the product selectivity and the reaction mechanism. Through these correlations, the cause of the observed differences in product selectivity depending on the reaction conditions are to be determined. Based on the obtained mechanistic insights, strategies to control the selectivity of cross Rauhut-Currier reactions will be developed, by choosing appropriate reaction conditions and/or by rational catalyst design. The potential of this new method is to be demonstrated by application to the synthesis of oleocanthal.

• DFG Programme: WBP Fellowship
• International Connection: United Kingdom
• Host: Professor Guy C. Lloyd-Jones, Ph.D.