Phosphate (Pi) and its anhydrides constitute
major nodes in metabolism. Thus, plant performance depends directly on
Pi nutrition. Inadequate Pi availability in the rhizosphere is a common
challenge to plants, which activate metabolic and developmental
responses to maximize Pi usage and acquisition. The sensory mechanisms
that monitor environmental Pi and transmit the nutritional signal to
adjust root development have increasingly come into focus. Recent
transcriptomic analyses and genetic approaches have highlighted complex
antagonistic interactions between external Pi and Fe bioavailability and
have implicated the stem cell niche as a target of Pi sensing to
regulate root meristem activity.
Kopycki, J.; Schmidt, J.; Abel, S.; Grubb, C. D. Chemoenzymatic synthesis of diverse
thiohydroximates from glucosinolate-utilizing enzymes from Helix pomatia
and Caldicellulosiruptor saccharolyticus Biotechnol Lett 33, 1039-1046, (2011) DOI: 10.1007/s10529-011-0530-y
Thiohydroximates comprise a diverse class of compounds important in both biological and industrial chemistry. Their syntheses are generally limited to simple alkyl and aryl compounds with few stereocenters and a narrow range of functional groups. We hypothesized that sequential action of two recombinant enzymes, a sulfatase from Helix pomatia and a β-O-glucosidase from Caldicellulosiruptor saccharolyticus, on glucosinolates would allow synthesis of thiohydroximates from a structurally broad array of abundant precursors. We report successful synthesis of thiohydroximates of varied chemical classes, including from homochiral compounds of demonstrated biological activity. The chemoenzymatic synthetic route reported here should allow access to many, if not all, of the thiohydroximate core structures of the ~200 known naturally occurring glucosinolates. The enrichment of this group for compounds with possible pharmacological potential is discussed.