Iodosobenzene and iodoxybenzene as reagents for oxygen transfer in organophosphorus chemistry

Article abstract of DOI:10.1055/s-2001-12312

The application of iodosobenzene (1) and iodoxybenzene (2) for the oxidation reaction of phosphorous, phosphorothiono and phosphoroseleno compounds into the corresponding ≡P(O) analogs is demonstrated. Retention of configuration at the phosphorus atom and full stereoselectivity of these reactions in model diastereoisomeric cis- and trans-2-phenylamino-2-thiono-4-methyl-1.3.2-dioxaphosphorinans (30) as well cis- and trans-2-phenylamino-2-seleno-4-methyl-1.3.2-dioxaphosphorinans (31) systems, are demonstrated.

Full text of DOI:10.1055/s-2001-12312

LETTER
505
Iodosobenzene and Iodoxybenzene as Reagents for Oxygen Transfer in
Organophosphorus Chemistry
Gra yna Mielniczak, Andrzej opusi ski*
Center of Molecular and Macromolecular Studies Polish Academy of Science, Sienkiewicza 112, 90-363 ód , Poland
E-mail: lopuch@bilbo.cbmm.lodz.pl
Received 8 January 2001
our results on the application of the readily available io-
doso- (1) and iodoxybenzene (2), for the oxidation of tri-
coordinated phosphorus compounds and their
Abstract: The application of iodosobenzene (1) and iodoxybenzene
2) for the oxidation reaction of phosphorous, phosphorothiono and
phosphoroseleno compounds into the corresponding P(O) analogs
(
is demonstrated. Retention of configuration at the phosphorus atom phosphothio and phosphoseleno analogues, which result
and full stereoselectivity of these reactions in model diastereoiso- in the formation of the corresponding P(O) compounds
meric cis- and trans-2-phenylamino-2-thiono-4-methyl-1.3.2-diox- (eq. 1). The results are shown in Table 1.
aphosphorinans (30) as well cis- and trans-2-phenylamino-2-
seleno-4-methyl-1.3.2-dioxaphosphorinans (31) systems, are dem-
onstrated.
Key words: oxidation, iodosobenzene, iodoxybenzene, organo-
phosphates
Equation 1
The search for efficient reagents and procedures for the
mild and selective transfer of oxygen to structurally dif-
ferent chemical compounds, is still in progress. The se-
1
The reactions were performed in acetonitrile solution at
room temperature without or in the presence of montmo-
rillonite K10 in 0.5 weight ratio in relation to 1 or 2, re-
spectively. The 31P NMR spectroscopy was used to
monitor the progress of the reactions.21
lective oxidation of heteroatoms like sulfur, selenium,
tellurium, nitrogen and phosphorus atoms incorporated in
2
-4
organic and bioorganic structures is of special interest.
Oxidative detoxification of organophosphorus com-
pounds including of VX agents is also an important and The oxidation reactions of P(III) compounds 3 and 5 by
5
current problem.
both 1 and 2 gave good yields. Whereas the reaction of tri-
ethyl phosphite (7) with either 1 or 2 was very slow even
in the presence of the activator (entries 5 and 6). Diethyl
phosphite (9) was relatively inert toward both oxidants 1
and 2 (entry 7, 9) under standard reaction conditions. The
formation of 40% of phosphate 10 is only observed after
180 hours reaction time (entry 8). On the other hand,
transformation of thionophosphorus compounds 11, 12
and 13 into the corresponding P(O) analogs occurred in
a few hours. Similarly, the phosphine selenide 16 as well
as selenophosphates 17 and 18 undergo very easy oxid-
ation by 1 and 2 with the formation of the desired P(O)
derivatives in excellent yields. It is interesting to note that
the double bond present in the organophosphorus sub-
strate 14 is not oxidized under these conditions (entry 20).
Aryl iodoso and iodoxy derivatives such as iodosoben-
zene (1) and iodoxybenzene (2) are common oxidants for
the conversion of alkynes to dicarbonyl compounds,
of alcohols into ketones or aldehydes and acids, as well
as for the synthesis of hydroxy ketones and oxidation
of sulfides to sulfoxides. The transformation of vicinal
6
,7
8
9
1
0
1
1
12
diols to carbonyl compounds by 1 and by 2 were also
reported. The catalyzed conversion of alkenes by 2 to –
1
3
carbonyl alkenes and dehydrogenation of ketones by m-
iodoxybenzoic acid providing carbonyl compounds were
1
4
also described.
Oxidation of organic sulfides by iodosobenzene (1)15 is
relatively slow and must be catalyzed for practical rea-
sons. Chromium, ruthenium and manganese complexes
or benzene selenenic acid were proposed as catalysts for
these transformations. In another work polyvalent iodine
compounds such as 2-dichloroiodobenzoic acid and io-
1
6
1
7
Reagents 1 and 2 were also tested in the oxidation reac-
tions of dialkyl monothiophosphoroate and dialkyl phos-
phorodithioate salts. The reaction of potassium
dineopentylphosphorothioate (19) with 1 in acetonitrile in
the presence of montmorillonite K10, 0.5 equiv. gave af-
ter 48 h only 24% yield of potassium dineopentylphos-
phate (20) together with unreacted 19. Under the same
reaction conditions, oxidation of triethylammonium di-
neopentyl phosphorothioate (21) resulted in the formation
dosobenzoic acid were used as activators in the oxidation
of organic sulfides by hydrogen peroxide.18
Recently, an efficient procedure for the oxidation of or-
ganic sulfides by iodosobenzene (1) and montmorillonite
K10 or bentonite KSF as activators was reported.19
In contrast to these known applications of iodoso and io- of a mixture of products (Scheme 1), among which the ex-
doxy arenes, their use as oxidants in organophosphorus pected triethylammonium dineopentyl phosphoroate (22)
chemistry has not been reported. Here, we wish to present was detected.
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06
G. Mielniczak, A. opusi ski
LETTER
Table 1 Oxidation of
compounds by 1 and 2
3
1
a) yields calculated from P spectra, in brackets are given yields after isolation; b) product contaminated by unreacted 7 (17%,
3
1
31
P 138); c) 37% of starting 9 (
P 7.8) was present; d) excess of 1 equiv of 1 after 1.5 h was added; e) 1:0.5 molar ratio of
13 to 2; f) excess of 1 equiv of 2 increased the yield of 8 to 89%; g) ref. 20; h) 1:0.5 molar ratio of 16 to 2
Scheme 1
Oxidation of ammonium diethyl phosphorothioate (25) aphosphorinanes (31) were selected as model compounds.
with 2 in the absence of montmorillonite K10 went in turn The stereochemistry of 30 and 31 as well as of the 2-oxo
selectively and provided diethoxyphosphinyl disulfide analog 32 has already been established.2 The individual
2,23
(
26) as the sole product. Similar oxidation of triethylam- isomers cis-30 and trans-31 were treated with iodosoben-
monium dineopentyl phosphorodithioate (27) proved zene (1) and with iodoxybenzene (2) in acetonitrile solu-
completely unselective either in the presence or in the ab- tion in the presence and in the absence of montmorillonite
sence of an activator (Scheme 2).
K10, 0.5 weight equivalent.
To examine the stereochemical course of the studied P=X The results of these experiments are detailed in Table 2
P=O (X = S, Se) transformations, cis- and trans-2-phe- and generalized in Scheme 3. As shown in Scheme 3, all
nylamino-2-thiono-4-methyl-1.3.2-dioxaphosphorinanes
the studied oxidations occurred with retention of configu-
(
30) and 2-phenylamino-2-seleno-4-methyl-1.3.2-diox- ration at the phosphorus atom.
Synlett 2001, No. 4, 505–508 ISSN 0936-5214 © Thieme Stuttgart · New York

LETTER
Iodosobenzene and Iodoxybenzene as Reagents for Oxygen Transfer
507
Scheme 2
Table 2 Stereochemistry of the oxidation of the cis, and trans-30 and 31 by 1 and 2
a) yields calculated from 31P spectra, in brackets are given yields after isolation; b) 1.5 equiv.; c) 3 equiv.; d) 2.5 equiv.;
e) 85% of starting trans-31 was present
configuration at phosphorus in oxidations of cis-30 and
trans-30 as well as their cis and trans 2-seleno analogs by
®
3
potassium permanganate (Oxone ) was earlier observed.
These results corresponds also well with related stereose-
III
V
lective oxidations of several P and P derivatives of the
6-29
4
-methyl-1.3.2-dioxaphosphorinan system.2 Our meth-
od compares well with other available procedures for such
oxidations.2
,3,5,26-34
References and Notes
(
1) Hudlicky, M. Oxidations in Organic Chemistry, ACS
Monograph 186, Washington 1990. R.Sreekumaraud, R.;
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Scheme 3
In conclusion, we have found that iodosobenzene (1) as
well as iodoxybenzene (2), in the presence of a montmo-
rillonite K10 can be conveniently used for the efficient
III
transformation of P , P=S and P=Se organophosphorus
compounds into their P=O derivatives. The oxidation is
fully stereoselective and takes place with retention of con-
figuration at the phosphorus atom. The retention of the
(
2) Uemura, S. Comprehensive Organic Synthesis, B. M. Trost, I.
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Synlett 2001, No. 4, 505–508 ISSN 0936-5214 © Thieme Stuttgart · New York

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G. Mielniczak, A. opusi ski
LETTER
(
(
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(0.5 mmol) in 2-3 mL acetonitrile was added to the stirred
3
1
suspension. After the reaction was completed ( P NMR) the
crude reaction mixture was filtered through Celite, the solvent
was removed in vacuo and the product was finally separated
by crystallization or flash chromatography on silica gel. The
identical procedure was applied to all the other oxidation
reactions performed on the 0.1 mmol to 0.6 mmol scale.
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(
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21) Typical experimental procedure for the 0.5 mmol scale: The
2
4
25
suspension of oxidant 1 or 2 (0.5 mmol) and
Article Identifier:
montmorillonite K10 used in weight ratio 1:0.5 to 1 or 2 were
stirred at room temperature in 2-5 mL of dry acetonitrile for
1437-2096,E;2001,0,04,0505,0508,ftx,en;G00201ST.pdf
Synlett 2001, No. 4, 505–508 ISSN 0936-5214 © Thieme Stuttgart · New York