Selective phosphorylation on primary alcohols of unprotected polyols

Article abstract of DOI:10.1080/10426500108040232

The triad tribenzylphosphite-iodine-pyridine offers a general selective method for phosphorylation reactions of primary alcohols of unprotected α-diols and polyols. A mechanistic study by ³¹P NMR allowed to evidence the formation, from iododibenzyl phosphate and pyridine, of a very reactive pyridinium salt intermediate. This analysis shows that pyridine behaves as a covalent catalyst like DMAP in acylation reactions from acylchloride. Due to its steric hindrance and high reactivity, this species appears to be the efficient selective phosphorylation reagent but leads to dibenzylphosphoric esters. Under mild conditions, the cleavage of benzyl groups gives monoester phosphoric acid.

Full text of DOI:10.1080/10426500108040232

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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SELECTIVE PHOSPHORYLATION
ON PRIMARY ALCOHOLS OF
UNPROTECTED POLYOLS
a
a
Sylvain Ladame , Samantha Claustre & Michèle
a
Willson
a
Groupe de Chimie Organique Biologique, LSPCMIB,
UMR CNRS 5068 Université Paul Sobatier, 31062,
Toulouse cédex 04, France
Version of record first published: 04 Oct 2006.
To cite this article: Sylvain Ladame , Samantha Claustre & Michèle Willson (2001):
SELECTIVE PHOSPHORYLATION ON PRIMARY ALCOHOLS OF UNPROTECTED POLYOLS,
Phosphorus, Sulfur, and Silicon and the Related Elements, 174:1, 37-47
To link to this article: http://dx.doi.org/10.1080/10426500108040232
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