Details of Grant 

EPSRC Reference:	EP/C543130/1
Title:	Harnessing Reactive Intermediates for Organic Synthesis
Principal Investigator:	Grainger, Dr RS
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	School of Chemistry
Organisation:	University of Birmingham
Scheme:	Standard Research (Pre-FEC)
Starts:	01 October 2005	Ends:	31 March 2009	Value (£):	249,163
EPSRC Research Topic Classifications:	Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:	Pharmaceuticals and Biotechnology
Related Grants:
Panel History:	Panel Date Panel Name Outcome 13 Apr 2005 Chemistry Fellowships Interview Panel Deferred 16 Mar 2005 Chemistry Fellowships Sift Panel 2005 Deferred
Summary on Grant Application Form
1. To investigate atropmisomerism in ortho-substituted anilines as a stereochemical control factor in the cyclisation of carbamoyl radicals2. To investigate the structural features which lead to sulfur monoxide transfer from peri-substituted trisulfide oxides, and use these results to prepare areagent capable of transferring sulfur monoxide at lower temperatures to a broader range of dienes.3. To investigate the dithiocarbamate group transfer cyclisation of carbamoyl radicals to carbon-nitrogen double bonds, carbon-nitrogen triple bonds, alkynes, and vinyl sulfones.4. To investigate functional group transformations of the dithiocarbamate group, particularly its ability to act as a leaving group in the formation of carbenes.A number of species in chemistry are too unstable to be isolated. Such species rapidly react with themselves, or with other molecules. However this high reactivity also makes them useful for building or synthesising molecules if this reactivity can be understood and controlled. In this work a number of such species will be investigated, some for the first time.Sulfur monoxide is a gas very similar in structure to oxygen in the atmosphere. In contrast to oxygen, sulfur monoxide is only fleetingly formed in the gas phase, rapidly reacting with itself to form sulfur dioxide and elemental sulfur. If we want to use sulfur monoxide as a reagent in organic synthesis, we cannot therefore get it out of a bottle, but must find a way to generate in the present of a suitable trap (typically an organic molecule called a diene). A new method of generating sulfur monoxide will be investigated in this research, based upon building up a strained organic molecule which can release its strain energy by breaking apart in a well-defined manner with the release of sulfur monoxide.Radicals are organic molecules containing an unpaired electron. This generally makes them highly reactive species, but they do react in a predictable and highly useful manner. Unfortunately many of the methods to generate radicals rely on the use of toxic tin reagents. In this project we will look at a new method of generating a certain class of radical, called an aminoacyl radical, which does not rely on tin reagents, but rather on light to initiate (start) the reaction. This molecules which can be prepared by this chemistry contain an amide bond, one of the key carbon - nitrogen bonds in chemistry, and ring systems, which are present in a large number of naturally occurring molecules and pharmaceuticals. The chemistry relies on a sulfur containing functional group called a dithiocarbamate which is transferred from one atom to another in the course of the reaction. New chemistry of the dithiocarbamate group will also be investigated in the course of this work, with the intention of using it to generate other reactive species, called carbenes.
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Organisation Website:	http://www.bham.ac.uk