Efficient New Organic Reagents for Electron Transfer

The over-arching aim of the project will be to design new 'green' chemistry that can be applied to the preparation of new types of molecules that are of interest in pharmaceutical chemistry. New ways to prepare interesting molecules are always needed. The key advantage of our reagents is that they consist of simple and economical earth-abundant elements, silicon, oxygen, hydrogen, nitrogen, and they avoid elements that cause environmental concerns.
This project will study the reactivity of new types of reductive and oxidative reagents that are of two classes: (i) radical anions and (ii) radical cations. Preliminary chemistry was published by the Murphy group in leading journals: Angew. Chem. Int. Ed. 2017, 56, 13747-13751. J. Am. Chem. Soc., 2016, 138, 15482-15487.
Detailed aims:
(i) The student will study the scope of reactions that have been recently discovered in the Murphy group, that use silane reagents in the presence of base; the reactions will be applied to molecules of pharmaceutical interest. These will be heterocycles such as pyridines, pyrimidines, oxazoles and pyrroles. No such studies have been conducted to date.
(ii) The student will study the mechanisms of these reactions. There is hot debate in the literature on the nature of the reactive species formed on mixing silanes with base. Accordingly, the student will probe for information about the nature of the reactions, by examining the chemical structures of the products and the by-products of the reactions and, where appropriate, by using physical organic chemistry methods (reaction kinetics, and the effect of modified reagents on the outcomes of the reactions) to verify proposals.
(iii) Based upon the information gleaned from aims (i) and (ii), the student will apply our reactions to new types of substrates. In this way, we will be predicting new reactivity using chemical expertise, and predicting how this can be applied to the design of new drug candidates.
(iv) We will look to computational chemistry (DFT = density functional theory) methods to select from the proposals on reaction mechanism that we make. The student will be able to avail of training in this area of chemistry.

The programme will provide broad training at the forefront of chemistry for the student engaged on the project. Our practice is to publish in world-leading journals, and we will wish to follow this practice in this project. The student will have the opportunity to attend and present research results at one or more international research meetings and will avail of a broad programme of modules provided by the University for professional and personal development.