3646-10-4Relevant articles and documents
H-tetraoxaspirophosphoranes as possible intermediates in the phosphonylation by phosphorous acid / oxiranes
Tzokov, Svetomir B.,Vassilev, Nikolay G.,Momtcheva, Rositza T.,Kaneti, Jose,Petkov, Dimiter D.
, p. 187 - 196 (2007/10/03)
The detailed 31P-NMR study of the mechanism of the ribozymomimetic phosphonylation with phosphorous acid / oxirane revealed consecutive formation of β-hydroxy H-phosphonate monoester, di-(β-hydroxyalkyl) H-phosphonate, alkylene H-phosphonate, β-hydroxyalkyl alkylene phosphite and the corresponding stereoelectronically stabilized pentacoordinated H-tetraoxaspirophosphorane. The equilibrium between the triphosphite and the spirophosphorane shifts towards the β-hydroxyalkyl alkylene phosphite at high temperatures. In the presence of alcohol and controlled amounts of water transesterification of the β-hydroxyalkyl alkylene phosphite to the corresponding alkyl alkylene phosphite, and hydrolysis to β-hydroxyalkyl alkyl H-phosphonate proceed at the elevated temperature. β-Hydroxyalkyl alkyl H-phosphonates are model compounds of the phosphodiester bond and undergo hydrolysis with a diol leaving in the presence of one equivalent of water.
ADDITIONS DES FONCTIONS >NH ET >P(O)H SUR LA DOUBLE LIAISON DES VINYL SPIROPHOSPHORANES SYNTHESE DES α ET β AMINO SPIROPHOSPHORANES ALCOOLYSE DE LA LIAISON P-C DANS LES COMPOSES D'ADDITION OBTENUS
Burgada, Ramon,Mohri, Ali
, p. 85 - 96 (2007/10/02)
Addition of amines and of hydrogenphosphonates on the carbon-carbon double bond belonging to vinylphosphoranes is examined.The stereochemistry and reactivity of the saturated adducts obtained is rationalized.Alcoholysis of the P-C bond is also studied.
