Cast iron catalysis: New catalytic protocols for carbon-phosphorus bond synthesis

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The importance of catalysis cannot be underestimated; it is responsible for 35% of the world's Gross Domestic Product and is one of the key processes needed to tackle some of the world's grand challenges. For example, catalysis is a fundamental tool for the efficient preparation of modern pharmaceuticals and agrochemicals, vital for a rapidly expanding world population. Catalysis also contributes to our future energy needs by enabling new methods of energy capture, storage and release. It is essential for a sustainable future not least because of the inherent ability to make chemicals in a more environmentally benign manner, allowing chemical reactions to run faster at lower temperature making the preparation of key chemicals easier and more cost efficient. While the Platinum Group Metals dominate this landscape, development of abundant Base Metal alternatives is urgently required to maintain and advance global development.This fellowship will specifically deliver new catalytic strategies for the preparation of phosphines. Phosphorus-containing motifs are crucial to a host of manufacturing sectors where they constitute the vast majority of ligands used by the fine chemicals and pharmaceutical industries. Phosphines are excellent organocatalysts, constitute a range of biologically relevant motifs and since antiquity, have been central to the agrochemical industry. Traditional methods of making phosphines are inadequate by modern standards of innovative research; they often generate vast amounts of chemical waste and are limited in the types of chemical architectures that can be accessed both through a restricted pool of 'reactive' phosphines and by the small number of classical phosphine-tolerant reactions available to the synthetic chemist. We therefore need new and efficient methods to make phosphines that will overcome these technological barriers. I seek to develop novel catalytic protocols that are atom economic, use inexpensive phosphorus sources and/or exploit some of the simplest forms of phosphorus, using them in a new way to build up large amounts of molecular complexity from the simplest possible starting materials. In order to achieve this I will use mechanistic investigations to unravel the finer details of the catalytic cycles involved and thus inform future reaction development. By using iron, the fourth most abundant element in the earth's crust, these new processes will have sustainability built-in from first principles. The challenge is clear; few examples of using iron in this way exist. I aim to change this.The aim:-Investigate iron catalysts in atom-economic phosphine synthesis, making molecules relevant to the pharmaceutical and agrochemical industries.-Use iron catalysis for the activation and subsequent controlled delivery of the simplest phosphines.-Develop iron photocatalysis for completely novel reactivity, complementary to traditional thermal processes.