Hypervalent iodine in synthesis. 49. A new effective synthesis of Se-phenyl O,O-dialkyl phosphoroselenoates with polymer-supported phenyliodine diacetate

Article abstract of DOI:10.1081/SCC-100000533

Se-phenyl O,O-dialkyl phosphoroselenoates have been prepared by the one-pot reaction of sodium O,O-dialkyl phosphorates, diphenyl diselenide, and polymer-supported phenyliodine diacetate (PPID).

Full text of DOI:10.1081/SCC-100000533

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HYPERVALENT IODINE IN SYNTHESIS. 49. A NEW
EFFECTIVE SYNTHESIS OF Se-PHENYL O,O-DIALKYL
PHOSPHOROSELENOATES WITH POLYMER-SUPPORTED
PHENYLIODINE DIACETATE
Da-Jun Chen a & Zhen-Chu Chen b
a Department of Chemistry, Zhejiang University at Xixi Campus, Hangzhou, 310028,
People's Republic of China
b Department of Chemistry, Zhejiang University at Xixi Campus, Hangzhou, 310028,
People's Republic of China
Version of record first published: 09 Nov 2006.
To cite this article: Da-Jun Chen & Zhen-Chu Chen (2001): HYPERVALENT IODINE IN SYNTHESIS. 49. A NEW EFFECTIVE
SYNTHESIS OF Se-PHENYL O,O-DIALKYL PHOSPHOROSELENOATES WITH POLYMER-SUPPORTED PHENYLIODINE DIACETATE,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:3,
421-424
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SYNTHETIC COMMUNICATIONS, 31(3), 421–424 (2001)
HYPERVALENT IODINE IN SYNTHESIS. 49.
A NEW EFFECTIVE SYNTHESIS OF
Se-PHENYL O,O-DIALKYL
PHOSPHOROSELENOATES WITH
POLYMER-SUPPORTED PHENYLIODINE
DIACETATE
Da-Jun Chen and Zhen-Chu Chen∗
Department of Chemistry, Zhejiang University at Xixi
Campus, Hangzhou, 310028, People’s Republic of China
ABSTRACT
Se-phenyl O,O-dialkyl phosphoroselenoates have been pre-
pared by the one-pot reaction of sodium O,O-dialkyl phosphorates,
diphenyl diselenide, and polymer-supported phenyliodine diacetate
(PPID).
Esters of O,O-dialkyl phosphoroselenoic acids are of particular importance
in the synthesis of selenium dependent enzymes and seleno-t-RNAs (1). Besides,
they also serve as selenophosphorylating reagents of alkynes (2). The literature
methods of preparing Se-phenyl O,O-dialkyl phosphoroselenoates include the
Arbuzove-type reaction of trialkyl phosphites with benzeneselenenyl bromide
or chloride (3,4), the benzeneselenation of mercury O,O-dialkyl phosphorates
with benzeneselenenyl bromide (3), or the action of lithium selenophenolate on
∗Corresponding author.
421
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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CHEN AND CHEN
O,O-dialkyl phosphoryl chlorides (2). However, they generally implicate tedious
procedures, and sometimes involve toxic reagents or require strict reaction condi-
tions. Therefore, there is a need to develop an efficient method for their preparation.
Recently, we found that phenyliodine dicarboxylates can oxidatively cleave
–
the Se Se bond in diaryl diselenides to form arylselenyl carboxylates, which can be
used as an electrophilic phenylselenating reagent. On the basis of this reaction, we
developed a convenient one-pot synthesis of selenosulfonates (5). In connection
with our studies on the synthetic application of polymer-supported phenyliodine
diacetate (PPID) (6), this previous find led us to extend the phenylselenation re-
action to sodium O,O-dialkyl phosphorates by utilizing the combinative reagent
of diphenyl diselenide and PPID. Such a reaction would provide a new one-pot
procedure for the synthesis of Se-phenyl O,O-dialkyl phosphoroselenoates.
In fact, simply stirring a mixture of PPID, diphenyl diselenide, and sodium
O,O-dialkyl phosphorate in methylene chloride at room temperature gave the de-
sired product, Se-phenyl O,O-dialkyl phosphoroselenoates, after workup and iso-
lation. The reaction is efficient and high-yielding, while variation of the alkyl
groups does not affect the readiness of this conversion.
CH2Cl2
P
I(OAc)2 + PhSeSePh + (RO)2P(O)Na
rt
(RO)2-P(O)SePh +
P
I
As usual, we also examined the regeneration and recycling of the polymer
reagent. The spent resin was collected by filtration and reoxidized with peracetic
acid. The regenerated resin was used to repeat the reaction with no loss of activity
(see Table 1, entry 3).
In summary, this reaction represents a new efficient method for the synthe-
sis of Se-phenyl O,O-dialkyl phosphoroselenoates. It has some advantages over
existing ones, such as accessible starting materials, mild reaction conditions, sim-
ple procedure, and better yields. Furthermore, the range of useful application of
polymer-supported phenyliodine diacetate in organic synthesis has been extended.
EXPERIMENTAL
1
IR spectra were recorded on PE-683 Spectrophotometer. H NMR spectra
were recorded on PMX-60 Spectrometer, using CCl4 as the solvent with TMS as
an internal standard.

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HYPERVALENT IODINE. 49
Table 1. Preparation of Se-phenyl O,O-dialkyl Phosphoroselenoates
423
Entry
R
Time (h)
Yield (%)a
1
2
3
4
5
6
7
Me
Et
Et
n-Pr
i-Pr
n-Bu
s-Bu
1
1
1.5
1
1
86
93
91b
88
85
85
83
1.5
1.5
a Yield of isolated product based on diphenyl diselenide.
b Regenerated PPID was employed in this case.
Materials. PPID were prepared by our previous reported method with the
same functional capacity 2.96 mmol/g (6).
General Procedure for the Synthesis of Se-phenyl O,O-dialkyl Phos-
phoroselenoates. A mixture of sodium O,O-dialkyl phosphorate (4.0 mmol),
diphenyl diselenide (0.5 mmol) and PPID (0.3 g) was stirred for the appropriate
time at room temperature. When the reaction was complete as detected by TLC,
ether was then introduced to remove the polymer for recovery. The filtrate was
washed with H2O, dried with MgSO4, and concentrated. The desired product was
seperated by preparative TLC (petroleum ether:EtOAc = 8:1).
Entry 1: oil. IR (film): 1585, 1490, 1450, 1260, 1185, 1020, 785, 740 cm−1
.
1H NMR: 7.83–7.17 (m, 5H), 3.67 (d, 6H, J = 12 Hz).
Entry 2: oil. IR (film): 1585, 1490, 1440, 1255, 1165, 1020, 970, 790, 745
1
cm−1. H NMR: 7.80–7.17 (m, 5H), 4.50–3.80 (m, H), 1.28 (t, 6H,
J = 6 Hz).
Entry 4: oil. IR (film): 1590, 1490, 1453, 1400, 1255, 1000, 740 cm−1. 1H
NMR: 7.75–7.12 (m, 5H), 4.20–3.71 (m, 4H), 1.92–1.35 (m, 4H), 0.95
(t, 6H, J = 6 Hz).
Entry 5: oil. IR (film): 1580, 1490, 1445, 1390, 1380, 1252, 975, 740
cm−1. 1H NMR: 7.83–7.12 (m, 5H), 5.00–4.35 (m, 2H), 1.25 (t, 12H,
J = 6 Hz).
Entry 6: oil. IR (film): 1585, 1490, 1450, 1390, 1255, 1150, 1125, 1000, 740
1
cm−1. H NMR: 7.70–7.06 (m, 5H), 4.26–3.65 (m, 4H), 1.90–0.60
(m, 14H).
Entry 7: oil. IR (film): 1580, 1475, 1440, 1380, 1250, 1170, 1125, 1110,
1090, 1025, 975, 740 cm−1. 1H NMR: 7.80–7.05 (m, 5H), 4.75–4.11
(m, 2H), 1.90–0.65 (m, 16H).

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CHEN AND CHEN
REFERENCES
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Received in Japan January 11, 2000

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