Stereo-selective synthesis of non-canonical gamma-hydroxy-alpha-amino acids by enzymatic carbon-carbon bond formation

Carbon-carbon (C-C) bond formation is the fundamental reaction type in organic synthesis. Biocatalytic methods for C-C bond formation have been limited to a few types of enzymes. In this report, we demonstrated the capability of a PLP-dependent enzyme ApUstD performing both C-C bond activation and asymmetric C-C bond formation, which resulted in non-canonical gamma-hydroxy-alpha-amino acids. The reaction showed high efficiency (conversion up to 98%), stereo-selectivity (ratio up to >97 : 3), a broad substrate scope (25 isolated examples) and significant simplicity. Our results have extended the biocatalytic function of PLP-dependent enzymes for asymmetric C-C formation.