High enantioselectivities have been achieved in asymmetric desymmetrization reactions of cyclic anhydrides using organocatalysts; however, a detailed understanding of the catalyst-substrate interations that account for the selectivity is lacking. We are preparing transition state analogues (TSAs) that mimic the presumed tetrahedral transition state in anhydride desymmetrization reactions, to use as mechanistic probes. TSA 3  was synthesized in a racemic form via a route featuring a ring-closing metathesis reaction using the second generation Grubbs catalyst. We are currently exploring enantioselective routes to the TSA. Once the enantiomers of 3  are resolved, their interaction with the catalyst will be explored by NMR methods.

Synthesis of a transition state analog for studying the asymmetric desymmetrization of cyclic anhydrides

247th National Meeting (2014)

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