Organocatalysis has proved to be particularly effective in the asymmetric desymmetrization (ASD) of cyclic anhydrides, but the correlation between selectivity and catalyst structure is not fully understood. We are preparing stable transition state analogues (TSAs) of this reaction to use as mechanistic probes for enhancing our understanding the transition state-catalyst interactions that are important for selectivity. After resolution, interactions between the TSA (3  ) enantiomers and organocatalysts will be studied by NMR methods. Here, we describe the preparation of a tricyclic TSA, featuring a Diels-Alder reaction between cyclopentadiene and a cyclic phosphinate ester (1  ) to give 2   (ca. yield = 39%; ca. endo:exo = 79:21). The structures were verified by two-dimensional NMR methods.

Syntheses of transition state analogs (TSAs) as mechanistic probes for organocatalytic desymmetrization reactions

247th National Meeting (2014)

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