Details of Grant 

EPSRC Reference:	GR/R82586/01
Title:	Generation of Chiral, Nonracemic 2-Aminoallyl Cations: Application in asymmetric [4+3] and [3+2] Cycloadditions
Principal Investigator:	Shipman, Professor M
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Department:	Chemistry
Organisation:	University of Exeter
Scheme:	Standard Research (Pre-FEC)
Starts:	01 November 2002	Ends:	31 August 2003	Value (£):	181,683
EPSRC Research Topic Classifications:	Asymmetric Chemistry Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:	Chemicals No relevance to Underpinning Sectors
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Summary on Grant Application Form
We will develop an approach to 2-aminoallyl cations by ring opening of the highly strained yet stable 2-methyleneaziridine ring system. These little studied transient species are expected to behave similarly to 2-oxyallyl cations, and provide very concise routes to functionalised cycloheptanes and cyclopentanes. We suggest that 2aminoallyl cations will offer significant advantages over their 2-oxyallyl cation counterparts. Firstly, control of absolute stereochemistry will be possible by the incorporation of a chiral, nonracemic substituent into the allylic cation. Secondly, the reactivity of the 2-aminoallyl cation will be tuneable by varying the nature of the activating group. Finally, the mild conditions required for the generation of the 2-aminoallyl cations, and the ease with which 2-methyleneaziridines can be functionalised, will allow this chemistry to be used in the context of complex natural product synthesis.After optimisation of encouraging preliminary results obtained in our laboratory, we will establish if homochiral 2-aminoallyl cations derived from chiral, nonracemic 2-methyleneaziridines can be used to effect enantiocontrolled [4+3] cycloadditions with dienes, and stepwise [3+21 cycloadditions with olefins. Both intermolecular and intramolecular variants of these processes will be evaluated. The use of Lewis acids, protic acids, alkylating agents and transition metals to effect the cycloadditions will be assessed. The concise synthesis of two moderately complex natural products (alkaloid KD-B, a-cuparenone) will be undertaken to exemplify this new chemistry.
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