H-tetraoxaspirophosphoranes as possible intermediates in the phosphonylation by phosphorous acid / oxiranes

Article abstract of DOI:10.1080/10426500008076540

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.

Full text of DOI:10.1080/10426500008076540

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Phosphorus, Sulfur, and
Silicon and the Related
Elements
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H-
TETRAOXASPIROPHOSPHORANES
AS POSSIBLE INTERMEDIATES
IN THE PHOSPHONYLATION
BY PHOSPHOROUS ACID/
OXIRANES
Svetomir B. Tzokov a d , Nikolay G. Vassilev b ,
Rositza T. Momtcheva a , Jose Kaneti c & Dimiter
D. Petkova a
a Laboratory of BioCatalysis , Institute of
Organic Chemistry, Bulgarian Academy of
Sciences , 1113, Sofia, Bulgaria
b Laboratory of Nuclear Magnetic Resonance ,
Institute of Organic Chemistry, Bulgarian
Academy of Sciences , 1113, Sofia, Bulgaria
c Laboratory of Physical Organic Chemistry ,
Institute of Organic Chemistry, Bulgarian
Academy of Sciences , 1113, Sofia, Bulgaria
d Department of Chemistry , The University
of Sheffield , Dainton Building, Brook Hill,
Sheffield, S3 7HF, UK E-mail:
Published online: 19 Dec 2006.
To cite this article: Svetomir B. Tzokov , Nikolay G. Vassilev ,
Rositza T. Momtcheva , Jose Kaneti & Dimiter D. Petkova (2000) H-
TETRAOXASPIROPHOSPHORANES AS POSSIBLE INTERMEDIATES IN THE
PHOSPHONYLATION BY PHOSPHOROUS ACID/OXIRANES, Phosphorus,

Sulfur, and Silicon and the Related Elements, 166:1, 187-196, DOI:
10.1080/10426500008076540
To link to this article: http://dx.doi.org/10.1080/10426500008076540
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