The biocatalytic oxidation of racemic O-S-dimethyl O-p-nitrophenyl phosphorodithioate 5 catalyzed by chloroperoxidase from Caldariomyces fumago resulted in the formation of the (-)-(S)-enantiomer of the corresponding oxon 4 and unoxidized substrate 5 with a (+)-(R)-configuration. Both compounds were obtained with very high enantiomeric excesses, 99.6% and 97%, respectively. The thionation reaction of the resulting (-)-(S)-oxon 4 with Lawesson's reagent gave (-)-(S)-phosphorodithioate 5 with full stereoselectivity, while the oxidation of unreacted substrate (+)-(R)-5 with iodoxybenzene afforded oxon (+)-(R)-4 with 94.9% ee.
|Titolo:||Biocatalytic oxidation of thiophosphoryl compounds : a new chemo-enzymatic approach to enantiomeric insecticidal thionophosphates and their oxons|
COLONNA, STEFANO (Ultimo)
|Settore Scientifico Disciplinare:||Settore CHIM/06 - Chimica Organica|
|Data di pubblicazione:||2009|
|Digital Object Identifier (DOI):||10.1016/j.tetasy.2009.07.031|
|Appare nelle tipologie:||01 - Articolo su periodico|