Catalytic Characterization of α‐Regioselective Halohydrin Dehalogenase from Novosphingobium resinovorum

Halohydrin dehalogenases are highly valuable biocatalysts for chiral compound synthesis due to their diverse catalytic capabilities and inherent stereoselectivity. Historically, research on halohydrin dehalogenases is confined to a limited number of enzymes. However, with the advent of advanced gene mining methods, a growing number of halohydrin dehalogenases have been discovered and characterized, revealing a diverse array of new structures and catalytic functions. While halohydrin dehalogenases predominantly exhibit β-regioselectivity in the ring-opening of styrene oxides, a few α-regioselective halohydrin dehalogenases have also been identified. In this study, a new α-regioselective halohydrin dehalogenase, HHDHnsr, is purified and analyzed, and its application in the azide-mediated α-regioselective azidolysis of styrene oxide is explored. The findings highlight the potential of HHDHnsr as α-regioselective biocatalyst for the asymmetric synthesis of β-azidoalcohols, offering valuable insights for the future identification of α-regioselective HHDHs in enzyme mining.