Details of Grant 

EPSRC Reference:	EP/C006054/1
Title:	Diastereoselective Formation of Cyclopentanes and Gamma-Lactones Mediated by Manganese(III)
Principal Investigator:	Burton, Professor JW
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Chemistry
Organisation:	University of Cambridge
Scheme:	Standard Research (Pre-FEC)
Starts:	19 September 2005	Ends:	31 December 2006	Value (£):	124,519
EPSRC Research Topic Classifications:	Asymmetric Chemistry
EPSRC Industrial Sector Classifications:	Chemicals
Related Grants:
Panel History:
Summary on Grant Application Form
The rapid and selective synthesis of biologically important molecules (e.g. pharmaceuticals) is an important and continuing goal for chemists. It is necessary to be able to make such molecules using efficient processes which, as far as possible, are environmentally benign. This proposal involves the development of an exceedingly mild method for the selective construction of a certain class of biologically relevant compounds (namely poly-substituted chiral cyclopentanes and gamma-lactones). There are many methods available for the synthesis of chiral cyclopentanes however the method to be developed within this proposal has the potential to be the most mild and straightforward method for the construction of such systems. Our preliminary results indicate that we can synthesise chiral cyclopentanes via a free radical process, simply by heating an appropriate compound in alcohol in the presence of manganese(III) acetate. This process is operationally straightforward to conduct and does not require any special experimental procedures. The formation of chiral cyclopentanes using free-radical chemistry has been previously reported. Most of these reports utilise organotin compounds to effect the desired transformation. Organotin compounds are highly toxic and present not only a disposal hazard but are often difficult to remove completely from the desired product. The use of manganese(III) acetate overcomes these issues; the manganese by-products are readily removed using standard techniques. Further important benefits of using manganese(III) acetate over organotin compounds include: the ability to produce more highly functionalised products which are therefore more readily transformed into the desired materials; the potential to use a wider variety of radical precursors which, not only adds flexibility to the synthesis, but also allows a wider variety of compounds to be synthesised. Both of these advantages will be fully explored in this research. Another process which may occur during manganese(III) acetate mediated reactions is the formation of heterocyclic rings (e.g. gamma-lactones). A further aim of this proposal is to develop a selective synthesis of gamma-lactones bearing up to four contiguous chiral centres using manganese(III) acetate chemistry. These molecules will contain one all carbon chiral centre (a quaternary centre). The selective synthesis of chiral molecules carrying quaternary centres remains a challenging area for synthetic organic chemists. Our aim is to develop a very mild method for the construction of such systems. We currently have an efficient route to a functionally-differentiated molecule bearing a quaternary centre which we believe has the potential to be a very valuable building block for organic chemists. The mild synthetic methods developed during the initial phases of this project will be demonstrated in the efficient syntheses of a variety of biologically and structurally interesting molecules. In summary, the aim of this proposal is to develop an exceptionally mild and operational simple method for the highly selective synthesis of cyclopentanes and gamma-lactones which will be applicable to a wide range of biologically and structurally interesting molecules.
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Organisation Website:	http://www.cam.ac.uk