Redox efficiency: Exploring the role of hydride shifts in organic chemistry
Lead Research Organisation:
University of Oxford
Department Name: Oxford Chemistry
Abstract
Chemistry, and the ability to make molecules, is a central subject that is at the heart of many different scientific endeavours. Organic chemistry is especially concerned with the reactivity of carbon in all of its different forms and can be viewed as a study of the chemistry taking place within living things. Organic chemists are constantly looking for new ways of designing and building new molecules (synthetic chemistry is essentially molecular architecture) with interesting and exciting properties. Novel organic molecules lie at the centre of the pharmaceutical industry and they can be designed to have useful biological activity and eventually for use as medicines.
The key aspect of our proposed research is a new route to carbocyclic molecules by using a rearrangement of hydrogen atoms within a molecule (known here as a hydride shift). This particular reaction allows us to control the placement of functionality with a complex molecule with great efficiency such that carbocyclic compounds, such as cyclohexenes and benzenes, can be made with great precision; and in this case the reaction uses key promoters to make reactions run in ways that are not possible without them. The complex and cyclic molecules generated by this new approach are found in many different compounds of value in both the academic and commercial world, and application of this new method will lead to both new science and new applications of organic molecules. Moreover, the development of powerful and efficient new chemical reactions has beneficial consequences for the environmental impact of the chemical processes involved (ie new reactivity with increased efficiency and reduced waste).
The novel chemistry proposed herein will lead to a new, efficient and powerful way of making cyclic compounds to control all aspects of the structures of the products formed: this will be of great benefit to both academia and industry who will be able to make interesting and useful molecules in new ways. We have engaged a project partner from the pharmaceutical industry so that the project will develop rapidly into areas that are of direct interest and value to industry.
The real advantage of this proposal is the development of cutting edge science and its application to solve problems that are relevant to chemical scientists around the world.
The key aspect of our proposed research is a new route to carbocyclic molecules by using a rearrangement of hydrogen atoms within a molecule (known here as a hydride shift). This particular reaction allows us to control the placement of functionality with a complex molecule with great efficiency such that carbocyclic compounds, such as cyclohexenes and benzenes, can be made with great precision; and in this case the reaction uses key promoters to make reactions run in ways that are not possible without them. The complex and cyclic molecules generated by this new approach are found in many different compounds of value in both the academic and commercial world, and application of this new method will lead to both new science and new applications of organic molecules. Moreover, the development of powerful and efficient new chemical reactions has beneficial consequences for the environmental impact of the chemical processes involved (ie new reactivity with increased efficiency and reduced waste).
The novel chemistry proposed herein will lead to a new, efficient and powerful way of making cyclic compounds to control all aspects of the structures of the products formed: this will be of great benefit to both academia and industry who will be able to make interesting and useful molecules in new ways. We have engaged a project partner from the pharmaceutical industry so that the project will develop rapidly into areas that are of direct interest and value to industry.
The real advantage of this proposal is the development of cutting edge science and its application to solve problems that are relevant to chemical scientists around the world.
People |
ORCID iD |
| Timothy Donohoe (Principal Investigator) |
Publications
Cheang D
(2025)
Dynamic Kinetic Resolution Allows Control of Remote Stereochemistry in Asymmetric Hydrogen Borrowing Alkylation
in Angewandte Chemie International Edition
| Description | This ongoing research has enabled the synthesis of key carbocyclic molecules in a new and efficient manner, using aluminium reagents and catalysts. We are in the process of extending the scope of the reaction itself, hoping to prepare important new molecules that are of interest to the pharmaceutical industry, and we have learned how to make single stereoisomers of the compounds that we prepare. We are also taking the opportunity to expand the chemistry of aluminium reagents, which are sustainable and earth abundant metals with a bright future in synthetic chemistry. |
| Exploitation Route | It is hoped that the chemical methodology that is being developed will be used by the chemical industry and academia to make key carbocyclic molecules of interest. We also aim to promote a resurgence of interest in aluminium reagents and their uses in organic synthesis. |
| Sectors | Healthcare Pharmaceuticals and Medical Biotechnology |