Nucleophilic attack by oxyanions on a phosphate monoester dianion: the positive effect of a cationic general Acid.
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.
Kirby
Anthony J
AJ
University Chemical Laboratory, Cambridge University, Cambridge CB2 1EW, UK. ajk1@cam.ac.uk
Lima
Marcelo F
MF
da Silva
Davi
D
Nome
Faruk
F