Comparison of phosphoramidites in phosphatidylinositol synthesis

Full text of DOI:10.1080/10426500213329

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Comparison of Phosphoramidites in
Phosphatidylinositol Synthesis
Yutaka Watanabe , Hirofumi Munetsugu , Keita Mizobuchi & Minoru Hayashi
To cite this article: Yutaka Watanabe , Hirofumi Munetsugu , Keita Mizobuchi & Minoru
Hayashi (2002) Comparison of Phosphoramidites in Phosphatidylinositol Synthesis,
Phosphorus, Sulfur, and Silicon and the Related Elements, 177:8-9, 2103-2104, DOI:
10.1080/10426500213329
To link to this article: http://dx.doi.org/10.1080/10426500213329
Published online: 27 Oct 2010.
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Date: 12 June 2016, At: 22:30

Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2103–2104
Copyright �C 2002 Taylor & Francis
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DOI: 10.1080/10426500290094080
COMPARISON OF PHOSPHORAMIDITES IN
PHOSPHATIDYLINOSITOL SYNTHESIS
Yutaka Watanabe, Hirofumi Munetsugu, Keita Mizobuchi,
and Minoru Hayashi
Ehime University, Japan
(Received July 29, 2001; accepted December 25, 2001)
We reported xylylene N,N-diethylphosphoramidite (XEPA, 2a) as
a promising phosphitylating agent. The diisopropyl version was
also prepared by Chapleur et al. Preparation and purification of
XEPA are easier than those of an acyclic analog, dibenzyl N,N-
diisopropylphosphoramidite 2b, and both reagents have an identical
reactivity and are commercially available, although the latter has been
more widely used than the former. We describe here usefulness of
XEPA by demonstrating selective phosphorylation of diol 1 via the
phosphite-pyridinium tribromide method using 4a derived from phos-
phoramidite 2a and transforming the resultant 1-O-phosphate P(1) to
phosphatidylinositol and phosphatidylinositol 4-phosphate.
FIGURE 1
Address correspondence to Yutaka Watanabe, Department of Applied Chemistry,
Faculty of Engineering, Ehime University, Matsuyama 790-8577, Japan.
2
103

2
104
Y. Watanabe et al.
TABLE I Phosphorylation of 1
The regioselective phosphorylation of 1 was examined in the presence
of pyridinium tribromide, 2,6-lutidine, and calcium sulfate using three
glyceryl phosphites 4 that were prepared by the reaction of the corre-
sponding phosphoramidite 2 with racemic 1,2-di-O-palmitoylglycerol 3
in the presence of tetrazole. Cyclic phosphite 4a showed the best result,
giving selectively the desired 1-O-phosphate P(1) in good yield. In the
case of phosphite 4b derived from 2b, a larger quantity of the phosphite
was required, and the selectivity and yield were lower.
Phosphate P(1) thus obtained was deprotected by the reaction with
pyridinium poly(hydrogen fluoride) followed by catalytic hydrogenoly-
sis to give PI. On the other hand, phosphitylation with 2a and oxidation
of P(1) followed by deprotection afforded PI(4)P.
FIGURE 2