Organocatalyzed asymmetric desymmetrization (ASD) reactions can provide efficient routes to prepare chiral synthetic building blocks from achiral feedstock. In order to gain a better understanding of how cinchona-alkaloid-based organocatalysts enable high enantioselectivity in the methanolysis of cyclic anhydrides, stable transition state analogues (TSAs) have been prepared which incorporate phosphonates to mimic the tetrahedral carbon of the substrate’s proposed transition state for this reaction (Figure 1). Here we describe the synthesis and resolution of TSA 2 and ent-2 and progress toward TSA 1, both of which are prepared via a common Diels-Alder adduct. We also report preliminary results from two-dimensional NMR spectroscopy studies aimed at providing insight into the interactions and affinities of our TSAs and catalysts.

Enantioselective organocatalysis: Synthesis and NMR studies of transition state analogues

253rd National Meeting (2017)

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