title: Asymmetric phosphorylation through catalytic P(III) phosphoramidite transfer: enantioselective synthesis of D-myo-inositol-6-phosphate.
abstract: Despite the ubiquitous use of phosphoramidite chemistry in the synthesis of biophosphates, catalytic asymmetric phosphoramidite transfer remains largely unexplored for phosphate ester synthesis. We have discovered that a tetrazole-functionalized peptide, in the presence of 10-Å molecular sieves, functions as an enantioselective catalyst for phosphite transfer. This chemistry in turn has been used as the key step in a streamlined synthesis of myo-inositol-6-phosphate. Mechanistic insights implicate phosphate as a directing group for a highly selective kinetic resolution of a protected inositol monophosphate. This work represents a distinct and efficient method for the selective catalytic phosphorylation of natural products.
authors.affiliation: Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT 06520-4900, USA.
authors.forename: Peter A
authors.initials: PA
authors.lastname: Jordan
authors.forename: Katherine J
authors.initials: KJ
authors.lastname: Kayser-Bricker
authors.forename: Scott J
authors.initials: SJ
authors.lastname: Miller
mesh_terms: D055162:Biocatalysis; D007202:Indicators and Reagents; D007295:Inositol Phosphates / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D009943:Organophosphorus Compounds / Q000737:chemistry / Q000378:metabolism*; D010766:Phosphorylation; D013237:Stereoisomerism
chemical_list: D007202:Indicators and Reagents; D007295:Inositol Phosphates; D009943:Organophosphorus Compounds; C434331:phosphoramidite