Dioxygenase Reactivity of Nonheme Iron Hybrid Catalysts in Asymmetric cis-Dihydroxylation and Indole Oxidation Reactions by Dioxygen

• Applicants: Professor Dr. Holger Dobbek; Professor Dr. Kallol Ray
• Subject Area: Biological and Biomimetic Chemistry ; Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 566809713

The present project aims to integrate chemical catalysts for asymmetric cis-dihydroxylation and indole oxidation reactions in a protein matrix. The overall goal is to create biohybrid catalysts with a very broad substrate scope involving both aromatic and aliphatic alkenes. These catalysts will provide a sustainable and greener alternative to Sharpless dihydroxylation reactions for the preparation of enantiomerically pure cis-vicinal diols. Notably, besides their major importance in organic synthesis, vicinal diols are also represented in the industrial production of bulk and fine chemicals. Simple diols like propylene glycol and ethylene glycol are applied as polyester monomers or anti-freeze agents and produced on a multi ton scale per year, while 1,2-hexanediol or 2,3-butanediol are important starting materials for the fine chemical industry. Furthermore, we want (1) to tune the reactivity of the chemical catalysts by controlling the environment around the catalyst, including the charges, (de)protonation events, substrate access and product egress, and (2) to increase the turnover number of labile synthetic catalysts by protecting them against inactivation. Efforts will be also dedicated to unraveling the reaction mechanism of the cis-dihydroxylation and indole oxidation reactions at the electronic structure level. Various forms of spectroscopic methods will be employed as the experimental means of making an unambiguous assignment of the electronic structure of the reaction intermediates by trapping them under transient or freeze quench conditions. The main objectives of the project will be 1) To initiate pioneering and world-leading studies on the development of green asymmetric cis-dihydroxylation catalysts, leading to the elucidation of reaction mechanisms and its application in large-scale organic synthesis. 2) To strengthen the growing links among leading international researchers, generating a tremendous synergy by exchanging knowledge and expertise of the Korean Research Laboratory (KRL) and German Research Laboratories (GRLs).

• DFG Programme: Research Grants
• International Connection: South Korea
• Partner Organisation: National Research Foundation of Korea, NRF
• Cooperation Partner: Professor Wonwoo Nam, Ph.D.