Details of Grant 

EPSRC Reference:	GR/R83002/01
Title:	Synthetic and Mechanistic Studies Involving Nitrogen-, Sulfur- and Silicon-Containing Radicals
Principal Investigator:	Roberts, Professor B
Other Investigators:
Researcher Co-Investigators:
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Department:	Chemistry
Organisation:	UCL
Scheme:	Standard Research (Pre-FEC)
Starts:	14 April 2002	Ends:	13 April 2004	Value (£):	128,152
EPSRC Research Topic Classifications:	Chemical Synthetic Methodology Physical Organic Chemistry
EPSRC Industrial Sector Classifications:	Chemicals Pharmaceuticals and Biotechnology No relevance to Underpinning Sectors
Related Grants:
Panel History:	Panel Date Panel Name Outcome 24 Jan 2002 Chemistry responsive January 02 Deferred
Summary on Grant Application Form
We propose to develop methodology for the synthesis of a variety of types of nitrogen-containing compound based on tin-free radical-chain reactions. The approach adopted throughout will be to seek mechanistic insight into the elementary reactions involved, in order to guide and diversify the project. The programme will be divided into two related parts. First, the strong influence of polar effects on the reactivities of electrically-neutral free radicals will be exploited in the design of thiol-mediated chain reactions of oxime ethers, aldohydrazones and related compounds that contain a C=N group to which radical addition to carbon can take place with formation of a new C-C bond. Reductive alkylation of these compounds will be developed using direct hydrogen-atom transfer to thiyl radicals from an electron-rich C-H bond as the source of alkyl radicals or an indirect route via an intermediate silyl radical, which yields the alkyl radical by reaction with an organic halide or thiocarbonyl compound. Related thiol-catalysed reactions of azo compounds and of azides will be investigated as new routes to amines and nitriles. Azides will also serve as sources of iminyl radicals, leading to imines (and thence to carbonyl compounds) and cyclised products such as delta 1-pyrrolines. In the second part of the project, reactions mediated by reactive silylaminyl and siloxyl radicals will be explored as novel rotes to epoxides and to aziridines, with the formation of new C-C bonds. These reactions will not require thiol catalysis and involve an addition/beta-scission sequence for the generation of silylaminyl and siloxyl radical intermediates.
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