Project description
Enhancing selectivity in phenol halogenation reactions
Phenols react with halogens, such as fluorine, chlorine and bromine, to yield mono-, di- or tri-substituted products. Funded by the Marie Skłodowska-Curie Actions programme, the ElectroPheX project aims to improve site selectivity in phenol halogenation reactions by using electrochemical methods. The interdisciplinary project will probe the ability of these methods to enhance both reaction selectivity and reactivity, focusing on the redox properties of catalysts, compounds, complexes and substrates, generating open-shell species and adjusting the oxidation state of metals.
Objective
ElectroPheX aims to develop electrochemically-mediated methods for the site-selective halogenation of phenols. Electrochemistry will be the main feature of this project as it can be an efficient way to access and manipulate reactive intermediates.
The project will span disciplines (interdisciplinarity) and aims to study electrochemistry’s ability to act as an enhancement tool for both selectivity and reactivity. Electrochemistry will help us to: (1) help us study the redox properties of catalysts, compounds, complexes and substrates (find redox potentials etc.); (2) to generate open-shell species; and, (3) to adjust the oxidation state of metals.
WP1-ORTHO focuses on (1) the design and synthesis of a series of compounds that contain N-halogen bond and they are capable of facilitating the ortho-halogenation of phenols upon anodic oxidation, (2) the study of intermolecular interactions and how the electrochemical generation of the corresponding radical-cation of N-halogen bond will alter/enhance the strength of the former.
WP2-META aims at the development of an electrochemically-mediated methodology for the meta-halogenation of phenols. Early transition metals (Mn, Co) will be used in order to facilitate the desired transformation. Electrochemistry will orchestrate the whole procedure giving access to adjacent oxidation states of metallic centers.
WP3-PARA targets para-halogenation of phenols mediated by a novel catalyst that mimics a main feature of photosystem II leading to a proton-coupled electron transfer (PCET) protocol for the transformation.
In WP4 the acquired knowledge will be translated to complex phenolic compounds in order to achieve a late-stage functionalization. SAR libraries, PET radiotracer, Also, the synthesis of highly site-selective halogenation of phenols can provide valuable intermediates for the preparation of poly-substituted arenes with a well-defined relationship between their substituent via cross-coupling reactions.
Fields of science
Keywords
Programme(s)
Funding Scheme
MSCA-IF - Marie Skłodowska-Curie Individual Fellowships (IF)Coordinator
45470 Muelheim An Der Ruhr
Germany