Nucleophilic carbenes as organocatalysts for asymmetric synthesis. Chemical compounds which come in two chiral mirror images (enantiomers) can have very different biological function. Often one form can have beneficial effects while the other can cause great harm (such as birth defects in the case of thalidomide). It is therefore very important for the drug industry to have asymmetric chemical reactions that lead specifically to only one enantiomer. The asymmetric reactions in this project ha ....Nucleophilic carbenes as organocatalysts for asymmetric synthesis. Chemical compounds which come in two chiral mirror images (enantiomers) can have very different biological function. Often one form can have beneficial effects while the other can cause great harm (such as birth defects in the case of thalidomide). It is therefore very important for the drug industry to have asymmetric chemical reactions that lead specifically to only one enantiomer. The asymmetric reactions in this project have been used previously to synthesise the anti-cancer metabolite roseophilin. The results of this project will ensure that there are many more similar success stories in the pharmaceutical and biotechnology industries.Read moreRead less
Exploring new roles for phosphorus radicals in health, environment, and technology. Several practical outcomes will arise from this project. Information on processes that contribute to genetic disease and cancer will be derived through studies of the role of phosphorus radicals in DNA damage. Processes that lead to the degradation of natural and synthetic materials in the environment will be explored. Clean reactions will be developed for the fabrication of advanced materials (e.g. pharmaceutica ....Exploring new roles for phosphorus radicals in health, environment, and technology. Several practical outcomes will arise from this project. Information on processes that contribute to genetic disease and cancer will be derived through studies of the role of phosphorus radicals in DNA damage. Processes that lead to the degradation of natural and synthetic materials in the environment will be explored. Clean reactions will be developed for the fabrication of advanced materials (e.g. pharmaceuticals). These innovations will expand Australia's international profile in a growing research area. The project will also address three of Australia's National Research Priorities, contribute to the training of researchers in Free Radical Chemistry, and initiate research collaborations with institutions in France and the USA.Read moreRead less
Hydrogen Abstraction in Chemical, Biochemical and Polymerization Processes. Hydrogen-abstraction reactions are of vital importance in the chemical, biochemical and polymerization processes that occur in everyday life. The objective of the proposed research is to improve our understanding of such reactions. State-of-the-art quantum chemistry calculations will be used to examine a broad range of hydrogen-abstraction reactions, and to obtain accurate information about the factors that influence suc ....Hydrogen Abstraction in Chemical, Biochemical and Polymerization Processes. Hydrogen-abstraction reactions are of vital importance in the chemical, biochemical and polymerization processes that occur in everyday life. The objective of the proposed research is to improve our understanding of such reactions. State-of-the-art quantum chemistry calculations will be used to examine a broad range of hydrogen-abstraction reactions, and to obtain accurate information about the factors that influence such reactions. Building on this work, more detailed case studies will be performed in two important areas: the hydrogen-abstraction steps in biochemical reactions mediated by coenzyme B12, and chain-transfer processes in conventional and controlled free-radical polymerization.Read moreRead less
Switchable and stereocontrolled photoredox catalysis. This project aims to develop new catalytic synthetic reactions for the rapid and more direct functionalisation of organic compounds under mild conditions with the use of visible light. An integrated experimental and computational approach will be used to design potent visible-light photocatalysts that retain the advantages of standard photoredox catalysis but with the added ability to intercept and, thus control, reactive intermediates in sit ....Switchable and stereocontrolled photoredox catalysis. This project aims to develop new catalytic synthetic reactions for the rapid and more direct functionalisation of organic compounds under mild conditions with the use of visible light. An integrated experimental and computational approach will be used to design potent visible-light photocatalysts that retain the advantages of standard photoredox catalysis but with the added ability to intercept and, thus control, reactive intermediates in situ. This will enable the control of stereochemistry in photoredox reactions – not possible with standard catalysts - and establish other useful synthetic transformations. These strategies will make it easier to prepare valuable classes of organic molecules – efficiently, safely, and cost-effectively.
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Computer-Aided Design of High-Performance Photocatalysts for Solar Hydrogen Production Based on Red Titanium Dioxide. Large-scale generation of energy by solar conversion is critical for future sustainability. This project aims to develop high performance materials to efficiently convert solar energy to hydrogen - a clean fuel. Starting from the newly developed material red titanium dioxide, novel strategies for improved photocatalytic materials will be proposed and evaluated by advanced computa ....Computer-Aided Design of High-Performance Photocatalysts for Solar Hydrogen Production Based on Red Titanium Dioxide. Large-scale generation of energy by solar conversion is critical for future sustainability. This project aims to develop high performance materials to efficiently convert solar energy to hydrogen - a clean fuel. Starting from the newly developed material red titanium dioxide, novel strategies for improved photocatalytic materials will be proposed and evaluated by advanced computational approaches. Key issues for solar-to-hydrogen conversion will be clarified. The materials, knowledge and strategies achieved by this project will dramatically enhance current solar technology and in particular will advance the development of low-cost hydrogen production from water. Read moreRead less
Characterising and exploiting hydrogen tunnelling in environmentally and medically important enzymes. Theory and experiment will be used to study environmentally and medically important enzymes, and quantify the role that hydrogen tunnelling plays in their activity. The project will determine the basis of their remarkable ability to catalyse chemical reactions, and to engineer and design more efficient proteins and pharmaceuticals.
Structural and mechanistic studies on manganese systems targeting catalytic water oxidation. Hydrogen fuel production from electricity and water sources, such as seawater, is the goal for this research. The present project addresses a key hurdle to be overcome to make this feasible - efficient water oxidation. This project will 'steal nature's secrets' in this by deciphering and mimicking the efficient natural enzyme process.
Chiral Catalysts by Rational Design. This project aims to integrate theory and experiment to design new catalysts for the synthesis of multi-stereocentre-containing molecules. Such molecules offer clear advantages in the area of drug design, owing to their potent and selective binding to biological targets, but a lack of available methods for their preparation currently limits their widespread use. This project will use theory to guide the discovery of new ways to make these molecules. It is exp ....Chiral Catalysts by Rational Design. This project aims to integrate theory and experiment to design new catalysts for the synthesis of multi-stereocentre-containing molecules. Such molecules offer clear advantages in the area of drug design, owing to their potent and selective binding to biological targets, but a lack of available methods for their preparation currently limits their widespread use. This project will use theory to guide the discovery of new ways to make these molecules. It is expected that detailed understanding of the factors that control stereocentre formation will be obtained from accurate theoretical modelling and will be applied to invent new catalysts that deliver improved performance and control over product structure.Read moreRead less
Seeing chemical reactions: Electron pairing and energetics along pseudo-reaction pathways from high-resolution X-ray diffraction data. This project aims to see the electron pairs in chemical reactions by extending high-resolution X-ray diffraction experiments on molecules frozen along their reaction pathway. This knowledge will help chemists to control a desired chemical synthesis leading to new prospects in drug design or material science.
Discovery Early Career Researcher Award - Grant ID: DE210100053
Funder
Australian Research Council
Funding Amount
$428,710.00
Summary
Computational Discovery & Design of New Catalytic Halogenophilic Reactions. Computational chemistry will be used to discover and predict new halogenophilic (halogeno = halogen; philic = like) substitution reactions (SN2X) catalysed by positively charged (cationic) catalysts. SN2X is a less known substitution reaction compared to accepted textbook nucleophilic (nucleo = electron-rich) substitution reactions. This proposal capitalises on previous theoretical-experimental understanding of a cation- ....Computational Discovery & Design of New Catalytic Halogenophilic Reactions. Computational chemistry will be used to discover and predict new halogenophilic (halogeno = halogen; philic = like) substitution reactions (SN2X) catalysed by positively charged (cationic) catalysts. SN2X is a less known substitution reaction compared to accepted textbook nucleophilic (nucleo = electron-rich) substitution reactions. This proposal capitalises on previous theoretical-experimental understanding of a cation-catalysed SN2X to develop new chemical reactions using SN2X synthetic strategies to access difficult-to-make molecules of potential medicinal relevance with heavily substituted carbon-carbon and carbon heteroatom bonds. Read moreRead less