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In chemistry and biology, cation-π interactions contribute significantly to many important transformations. In sharp contrast, reactions accomplished with support from the complementary anion-π interactions are essentially unknown. In this report, we show that anion-π interactions can determine the selectivity of the enolate chemistry of malonate half thioesters. Their addition to enolate acceptors is central in natural product biosynthesis but fails without enzymes because non-productive decarboxylation dominates. The newly designed and synthesized anion-π tweezers invert this selectivity by accelerating the disfavored and decelerating the favored process. The discrimination of anionic tautomers of different planarization and charge delocalization on π-acidic surfaces is expected to account for this intriguing "tortoise-and-hare catalysis." Almost exponentially increasing selectivity with increasing π acidity of the catalyst supports that contributions from anion-π interactions are decisive.

Selective acceleration of disfavored enolate addition reactions by anion–π interactions