Identification and Structure Analysis of an Unusual Halohydrin Dehalogenase for Highly Chemo‐, Regio‐ and Enantioselective Bio‐Nitration of Epoxides
Hui‐Hui Wang, Nan‐Wei Wan, Run‐Ping Miao, Cheng‐Li He, Yong‐Zheng Chen, Zhi‐Qiang Liu, Yu‐Guo Zheng
Abstract
We report the discovery of an unusual halohydrin dehalogenase, HHDHamb, that can work under relatively low acidic conditions and extremely low temperatures for the bio-nitration of epoxides using nitrite as a nitrating agent. The bio-nitration strategy exhibits high chemo-, regio-, and enantioselectivity, catalyzing the kinetic resolution of various epoxides to enantiopure β-nitroalcohols with nitro-bearing stereocenters in up to 41 % isolated yield and >99 % enantiomeric excess (ee). Additionally, the bio-nitration method displays a high reaction efficiency and can be performed on a gram scale. We also solved the crystal structure of HHDHamb to understand the possible structural determinants of chemoselectivity control in the bio-nitration reaction.