Forming All‐Carbon Quaternary Stereocenters by Organocatalytic Aminomethylation: Concise Access to β2,2‐Amino Acids

The asymmetric synthesis of β 2,2 -amino acids remains a formidable challenge in organic synthesis. We report here a novel organocatalytic enantioselective aminomethylation of ketenes with stable and readily available N,O-acetals, providing β 2,2 -amino esters bearing an all-carbon quaternary stereogenic center in high enantiomeric ratios with a catalytic amount of chiral phosphoric acid. Typically, this transformation probably proceeds through an asymmetric counter-anion-directed catalysis. As a result, a concise, practical and atom-economy protocol toward rapidly access to β 2,2 -amino acids has been developed.