Asymmetric Dual-Reagent Catalysis: Mannich-type Reactions Catalyzed by Ion Pair

The combination of a new bifunctional phosphine and an acrylate generate a zwitterion in situ and it serves as an efficient catalyst for asymmetric reactions through a homogeneous ion‐pairing mode. This new catalytic system has been successfully applied to Mannich‐type reactions to give excellent results and it demonstrates a broad substrate scope. Such reactivity is not accessible with general organophosphine catalytic modes. Preliminary investigations into the mechanism are also presented. Paired off: A new strategy combines a chiral phosphine with methyl acrylate to form a homogeneous ion pair. This activation mode has been successfully applied to Mannich‐type reactions, thus generating a variety of fluorinated amino acid derivatives in high yields and with high ee values.