title: Nucleophilic attack by oxyanions on a phosphate monoester dianion: the positive effect of a cationic general Acid.
abstract: The two negative charges on a phosphate monoester RO-PO32- at neutral pH provide a considerable electrostatic barrier toward reactions with nucleophilic reagents with a negative charge on the attacking atom. Electrostatic repulsion disappears when the hydrolysis of an aryl phosphate monoester is catalyzed by a neighboring cationic general acid. The hydrolysis of 8-dimethylammonium-1-phosphate (1) is catalyzed by oxyanions, fluoride anion, and hydroxylamines at similar rates.
authors.affiliation: University Chemical Laboratory, Cambridge University, Cambridge CB2 1EW, UK. ajk1@cam.ac.uk
authors.forename: Anthony J
authors.initials: AJ
authors.lastname: Kirby
authors.forename: Marcelo F
authors.initials: MF
authors.lastname: Lima
authors.forename: Davi
authors.initials: D
authors.lastname: da Silva
authors.forename: Faruk
authors.initials: F
authors.lastname: Nome