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Bioinspired Oxidation of Hydrocarbons in Confined Spaces

Project description

Mimicking metalloenzymes to functionalise C-H bonds

Functionalising select C-H bonds in hydrocarbons is an ongoing challenge in chemical synthesis. Previous efforts have focused on emulating the metallic centre of enzymatic oxidation reactions. The EU-funded ConfiMet project will go beyond this by also incorporating secondary coordination effects, molecular recognition and confinement within the isolated active site of the protein. To do this, well-established coordination manifolds for the iron- and manganese-based oxidation of C-H bonds will be melded to a synthetic molecular receptor. The resulting metallo-cavitand receptors will feature a reactive metal centre in close proximity to a binding pocket with robust molecular recognition features. These site-selective functionalisation reactions in molecules with multiple chemically equivalent C-H bonds can enable sustainable production methods for drugs and other chemical specialties.

Objective

Selective functionalization of C-H bonds in hydrocarbons is a grand challenge that chemists have tried to address for decades drawing inspiration from enzymatic oxidation reactions, with limited success. The mimicry of metalloenzymes has typically focused on the metal center, overlooking crucial aspects of the enzymatic machinery: secondary coordination effects, molecular recognition, and confinement within the isolated active site of the protein.
Herein, well-established coordination manifolds for Fe- and Mn-based oxidation of C-H bonds will be melded to a synthetic molecular receptor. The novelty of the resulting metallo-cavitand receptors lies in the positioning of the reactive metal center in close proximity to a binding pocket with robust molecular recognition features. The proposed reactions will exploit a structured microenvironment based on carefully designed non-covalent interactions. The designed hosts will bind hydrocarbons and related substrates in a confined space in close proximity to a reactive metal species, promoting site-selective oxidation dictated by the orientation of the substrate within the receptor rather than by the innate reactivity of the different C-H bonds in the structure.
ConfiMet will deliver unprecedented site-selective functionalization reactions in molecules with multiple chemically equivalent C-H bonds, of important impact in the development of sustainable production methods for drugs and other chemical specialties.
This project is a unique opportunity for the researcher to combine existing skills in coordination chemistry and transition metal catalysis with supramolecular chemistry concepts. The stimulating environment provided by the Institute of Computational and Catalysis, a research unit of excellence at Universitat de Girona (Spain), will allow the candidate to develop leadership, communication, and independent thinking skills, enhancing her career prospects in the transition to an independent academic position.

Coordinator

UNIVERSITAT DE GIRONA
Net EU contribution
€ 181 152,96
Address
PLACA SANT DOMENEC 3
17004 Girona
Spain

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Region
Este Cataluña Girona
Activity type
Higher or Secondary Education Establishments
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Total cost
No data

Partners (1)