Specificity and Stereoselectivity of Cryptic Sulfotransferases

Sulfotransferases (STs) are ubiquitous enzymes found in all living organisms. These enzymes convert amines to sulfamates, and alcohols to sulfates, on a wide variety of biologically relevant molecules. Herein, we describe the characterization of a new subclass of ST that has been shown to facilitate the biosynthesis of azabicyclo[3.1.0] hexane (ABCH) natural products. We find that ST enzymes Fic28, Vzb21, and Azi31, enable stereoselective sulfation reactions on a variety of natural and unnatural amino alcohol substrates. We also demonstrate the chemoenzymatic conversion of these amino alcohols into chiral NH-aziridines. This reactivity accesses previously untapped substrates for sulfotransferases, with potential use in biocatalysis, resolution of racemic amino alcohols, and aziridination.