Control of phosphoryl migratory transesterifications allows regioselecive access to sugar phosphates
Mitul K Patel1, Benjamin G Davis
1Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
None:
Phosphate esters in polyhydroxylated systems are normally blighted by uncontrolled migration under a variety of reaction conditions. Cesium fluoride is demonstrated as a reagent to control migration of primary phosphates during transesterifications. This allows easy exchange of phosphoryl protecting groups enabling enhanced synthetic strategic flexibility and regioselective phosphate installation. Mechanistic analysis suggests that a fluoride-induced extended solvent sphere modulates steric bulk at phosphorus to favor the primary position.
Related Concept Videos
Phosphorylation
During phosphorylation, protein kinases transfer the terminal phosphate group of ATP to specific amino acid side chains of substrate proteins. Serine, threonine, and tyrosine are the most commonly...
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
SN2 Reaction: Stereochemistry
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
ATP Energy Storage and Release
One example of energy coupling using ATP involves a...


