The development of catalytic Mitsunobu reactions
Lead Research Organisation:
University of Nottingham
Department Name: Sch of Chemistry
Abstract
One of the major challenges facing chemists and chemical engineers today is the development of clean, energy efficient processes. Inherent in this problem is the necessity to selectively form chemical bonds under environmentally benign conditions. We propose to develop catalysts which will mediate clean, atom efficient versions of a family of chemical reactions used in academic and industrial laboratories worldwide. These reactions currently produce two molecules of waste for every molecule of product generated. In contrast, the only waste product produced by the proposed catalytic chemistry is water. The proposed research will result in cleaner chemical reactions which will be widely used in academic and industrial laboratories and is fundamentally significant to the fields of catalysis and green chemistry.
Planned Impact
The proposed research involves the development of catalytic reactions for the formation of carbon-heteroatom bonds under environmentally benign conditions. Broadly speaking, the new chemistry will reduce the environmental impact of producing fine chemicals by eliminating the waste products formed by an important family of chemical reactions. Given that the existing wasteful protocols are used in academic and industrial laboratories worldwide the work will have considerable environmental and economic impact in both the private sector and academia. The research will be of direct benefit to all scientists involved in the synthesis of fine chemicals, pharmaceuticals and agrochemicals. In the first instance applications of the chemistry for the synthesis of drug candidates will be pursued with pharmaceutical collaborators such as Pfizer, GSK, AstraZeneca, Novartis, and Syngenta. The School of Chemistry has an excellent working relationship with the pharmaceutical industry which was highlighted during the School's RAE feedback. The applicant will ensure that promising catalysts are made available to potential collaborators so that new applications of the chemistry can be investigated. Our dissemination plans, which include publication and participation at national and international chemistry meetings, will ensure that the new chemistry, and its applications, is visible to a wide range of potential users. We believe that proof-of-concept for the new catalytic chemistry can be obtained during the funding period and that our timescales are realistic for a project of this type. The proposed research is fundamentally significant to the fields of catalysis, synthesis and green chemistry and will establish the applicant as being internationally leading in these areas. The School of Chemistry has its own local Business Partnership Unit (BPU) that is responsible for promoting and supporting knowledge exchange (KE) activity within the School. In addition to fostering and supporting links and collaborations with a wide cross section of industry, the unit has a strong track record of delivering KE outcomes and leverages the resources available within the University Technology Transfer Office. Finally, the complex analysis and problem solving skills as well as the synthetic expertise required for a project of this type will enhance the employability of the postdoctoral research staff involved.
Organisations
Publications
An J
(2013)
Phosphorus(V)-catalyzed deoxydichlorination reactions of aldehydes
in Tetrahedron
An J
(2014)
The development of catalytic nucleophilic substitution reactions: challenges, progress and future directions.
in Organic & biomolecular chemistry
Denton R
(2012)
Phosphonium salt-catalysed synthesis of nitriles from in situ activated oximes
in Tetrahedron
Denton RM
(2010)
Phosphine oxide-catalysed chlorination reactions of alcohols under Appel conditions.
in Chemical communications (Cambridge, England)
Denton RM
(2010)
Catalysis of phosphorus(V)-mediated transformations: dichlorination reactions of epoxides under Appel conditions.
in Organic letters
Denton RM
(2011)
Catalytic phosphorus(V)-mediated nucleophilic substitution reactions: development of a catalytic Appel reaction.
in The Journal of organic chemistry
Tang X
(2014)
A procedure for Appel halogenations and dehydrations using a polystyrene supported phosphine oxide
in Tetrahedron Letters
Tang X
(2014)
Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes.
in Chemical communications (Cambridge, England)
Description | The key findings of the project were that certain phosphine oxides could be transformed into dioxyphosphoranes. This opens up the possibility for the catalysis of many different phosphorus(V)-mediated reactions. |
Exploitation Route | Results generated led to funding from GlaxoSmithKline and Syngenta via CASE collaborations. |
Sectors | Pharmaceuticals and Medical Biotechnology |
URL | http://dentonchemistry.com/research-2/ |
Description | Within academia our findings have formed the basis of at least ten publications from other research groups which build upon our work. Some of the methods that we developed for the synthesis of alkyl chlorides are being used in pharmaceutical research laboratories for chemical synthesis of drug candidates. |
First Year Of Impact | 2013 |
Sector | Pharmaceuticals and Medical Biotechnology |
Impact Types | Societal,Economic |