Osmium on chelate resin: Nonvolatile catalyst for the synthesis of DIOLS from alkenes

Article abstract of DOI:10.1055/s-0034-1379990

Osmium tetraoxide (OsO₄) was immobilized on a commercially available chelate resin DIAION CR11 (CR11) just by simply immersing it in a methanol solution of OsO₄ at room temperature. The resulting purple solid, 5% Os/CR11, indicated no volatility, and effectively catalyzed the oxidation of various alkenes to the corresponding diols.

Full text of DOI:10.1055/s-0034-1379990

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© Georg Thieme Verlag Stuttgart · New York
2015, 26, 700–704
letter
700
Y. Monguchi et al.
Letter
Synlett
Osmium on Chelate Resin: Nonvolatile Catalyst for the Synthesis
of Diols from Alkenes
Yasunari Monguchi*a
Fumika Wakayamaa
5% Os/CR11 (1 mol%)
NMO (1.1 equiv)
R2
Hitoshi Takadab
Yoshinari Sawamaa
Hironao Sajiki*a
acetone–H2O (7:3), r.t.
R2
OH
R3
R3
R1
R1
5% Os/CR11 (5 mol%)
NMO (1.5 equiv), H2O (2 equiv)
H
OH
75–100%
t-BuOH, r.t., leaching Os <1%
a Laboratory of Organic Chemistry, Gifu Pharmaceutical
University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan
monguchi@gifu-pu.ac.jp
sajiki@gifu-pu.ac.jp
b Organo Corporation, 4-4-1 Nishionuma, Minami-ku,
Sagamihara, Kanagawa 252-0332, Japan
Received: 07.12.2014
Accepted after revision: 18.12.2014
Published online: 20.01.2015
Chelate resins have been used for the purification of wa-
ter due to their metal-capturing ability based on the tight
coordination (complexation) by some functional groups on
the polymer backbone.20 DIAION CR11 (CR11), which is a
commercially available chelate resin manufactured by the
Mitsubishi Chemical Corporation, possesses iminodiacetic
acid moieties on the polystyrene-divinylbenzene-based
polymer,21 and the metal-CR11 complexes would be ex-
pected to be used as catalysts for organic reactions, since
the CR11 is a proven and standardized industrial product
with a stable supply. We have recently and successfully im-
mobilized copper species on CR11 as a complex (12%
Cu/CR11) and developed a solvent-free Huisgen triazole
synthetic method using monosubstituted alkynes and
azides.22 In this paper, the application of the CR11 as the
support for the preparation of osmium catalyst and its ef-
fective use for the oxidation of alkenes as a nonvolatile and
easily prepared and handled catalyst are demonstrated.
CR11 was immersed in a pale yellow solution of OsO4 in
methanol, and the mixture was gently stirred at room tem-
perature under an argon atmosphere for three days. The
solution turned green, blue, gray, and finally colorless, and
the colorless CR11 was integrally empurpled, which was
collected on the filter paper, washed with methanol, and
dried under the reduced pressure (Scheme 1). The induc-
tively coupled plasma atomic emission spectrometry (ICP-
AES) analysis of both the resulting filtrate and methanol
wash detected a very low level of the residual osmium spe-
cies [1 mg/L (only 0.13% of the original OsO4 amount)]. This
result indicated that the osmium species were nearly quan-
titatively supported on CR11, and the osmium content of
the purple CR11 was determined to be 4.6 weight% (5%
Os/CR11).23,24
DOI: 10.1055/s-0034-1379990; Art ID: st-2014-u1011-l
Abstract Osmium tetraoxide (OsO4) was immobilized on a commer-
cially available chelate resin DIAION CR11 (CR11) just by simply im-
mersing it in a methanol solution of OsO4 at room temperature. The re-
sulting purple solid, 5% Os/CR11, indicated no volatility, and effectively
catalyzed the oxidation of various alkenes to the corresponding diols.
Key words chelate resin, diols, osmium, oxidation, supported catalyst
The osmium tetraoxide (OsO4)-catalyzed oxidation of
alkenes in the presence of a stoichiometric amount of a co-
oxidizing reagent, such as N-methylmorpholine N-oxide
(NMO) and tert-butyl hydroperoxide (TBHP), is one of the
most useful reactions for easy access to the corresponding
1,2-alkanediols.1 OsO4 (CAS registry number, 20816-12-0)
is commercially available as an aqueous solution or a solid
in a sealed ample due to its highly toxic and volatile nature.
Thus, OsO4 fundamentally possesses problems with its han-
dling and safety that need to be solved. The immobilization
of OsO4 on supports is the usual solution to such problems,
as represented by microencapsulated OsO4 using polysty-
rene2a (MC OsO4)2b, phenoxyethoxymethylpolystyrene3a,b
(PEM-MC OsO4),3c and acryronitrile-butadiene-polysty-
rene4 based on pioneering research by Kobayashi et al. Both
organic materials, such as polystyrene derivatives (bearing
ammonium salts,5 imidazolium salts,6 or amines7), polyani-
line,8 polysulfone,9 PEG-polyvinyl pyridine,10 polysilox-
ane,11 polyacylquinine-acrylonitrile,12 Amberlite,13 and
dendrimer14 derivatives, and inorganic materials, such as
silica gel,15 zeolite,16 molecular sieves,17 aluminum-magne-
sium hydroxide layer,18 and magnesium oxide,19 have been
used as supports of heterogeneous osmium catalysts.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 700–704

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Y. Monguchi et al.
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1) OsO4
also be decreased to 1.1 equivalents when using 1 mol% of
5% Os/CR11, and the desired diol was obtained in 89% yield
(Table 2, entry 5). On the other hand, the use of the catalyst
and NMO could hardly be reduced in t-BuOH regardless of
the presence (2 equiv) or absence of water (Table 2, entry 7
vs. 8 and entry 9 vs. 10).
MeOH, r.t., 3 d
DIAION CR11
5% Os/CR11
2) filtration, wash
3) drying
Scheme 1 Simple and easy preparation of 5% Os/CR11
While the oxidation of styrene (250 μmol) as a substrate
hardly proceeded in acetone (0.5 mL) for five hours in the
presence of 5% Os/CR11 (5 mol%) and NMO (1.5 equiv vs.
substrate) as a co-oxidant, the reaction efficiency was sig-
nificantly improved by the addition of water (0.1–0.2 mL
out of 0.5 mL, Table 1, entry 1 vs. entries 2–4).25 Too much
water (0.2 mL out of 0.5 mL) tended to decrease the yield of
the desired diol (Table 1, entry 2). The reaction progress in
t-BuOH as a solvent was also affected by the water use (Ta-
ble 1, entries 5–8). The addition of two equivalents of water
(to styrene, 500 μmol, 9.0 μL) in t-BuOH (0.5 mL) led to a
highest yield of the desired product (Table 1, entry 8), while
the reaction efficiency decreased by the addition of more
water (Table 1, entries 6 and 7). Furthermore, the use of
TBHP (70% in H2O) or potassium ferricyanide instead of
NMO was not effective for the present 5% Os/CR11-cata-
lyzed oxidation in 70% aqueous acetone (Table 1, entries 9
and 10).
Table 2 Quantity of 5% Os/CR11 and NMO for the 5% Os/CR11-Cata-
lyzed Oxidation of Styrene
5% Os/CR11
OH
NMO
Ph
OH
solvent (0.5 mL), r.t., 5 h
Ph
(0.25 mmol)
Entry
Os (5%)/CR11 NMO
Solvent
Yield (%)a
(mol%)
(equiv)
1
2
5
1.5
1.5
1.5
1.5
1.1
1.0
1.5
1.5
1.5
1.5
acetone–H2O (7:3)
acetone––H2O (7:3)
acetone–H2O (7:3)
acetone–H2O (7:3)
acetone–H2O (7:3)
acetone–H2O (7:3)
t-BuOH
75
1
77
3
0.8
0.5
1
72
4
37
5
89 (82)b
74
6
1
7
5
74
8
1
t-BuOH
41
Table 1 Evaluation of Solvent and Oxidant for the 5% Os/CR11-Cata-
lyzed Oxidation of Styrene
9c
10c
5
t-BuOH
81
1
t-BuOH
41
a Determined by 1H NMR spectroscopy using 1,3-benzodioxole as the inter-
nal standard.
5% Os/CR11 (5 mol%)
OH
oxidant (1.5 equiv)
b Isolated yield is shown in parentheses.
Ph
OH
c Conditions: 2 equiv of H2O (9.0 μL) were added.
solvent (0.5 mL), r.t. , 5 h
Ph
(0.25 mmol)
Entry
Solvent
Oxidant
Yield (%)a
trace
60
The substrate generality of the oxidation was confirmed
by the combined use of 5% Os/CR11 (1 mol%) and NMO (1.1
equiv) in 70% aqueous acetone at room temperature (Table
3, entries 1–10).26 Monosubstituted alkenes were good sub-
strates, and the desired diols were obtained in excellent
yields within short times (Table 3, entries 1–5). The reac-
tion efficiency was also found to be quite high regardless of
the geometry or cyclic/acyclic structure of the di- or trisub-
stituted alkenes (Table 3, entries 6–10). The 5% Os/CR11 in-
dicated the same or a slightly more efficient catalyst activi-
ty compared to OsO4 in 70% aqueous acetone (Table 3, en-
tries 1, 5, and 9). The reaction conditions using t-BuOH as a
solvent were also applicable to the dihydroxylation of vari-
ous alkenes in the presence of H2O (2 equiv) (Table 3, en-
tries 11–14).27
1
2
acetone
NMO
NMO
NMO
NMO
NMO
NMO
NMO
NMO
TBHP
acetone–H2O (6:4)
acetone–H2O (7:3)
acetone–H2O (8:2)
t-BuOH
3
75
4
70
5
74
6
t-BuOH–H2O (8:2)
t-BuOH–H2O (9:1)
t-BuOH–H2O (2 equiv)b
acetone–H2O (7:3)
acetone–H2O (7:3)
64
7
74
8
81
9
43
10
K3[Fe(CN)6]
0
a Determined by 1H NMR using 1,3-benzodioxole as the internal standard.
b Conditions: 9.0 μL H2O was used.
The volatility of 5% Os/CR11 was next investigated in
comparison to 4% aqueous OsO4 using a similar technique
reported by Kobayashi et al.2a,3a 5% Os/CR11 and 4% aqueous
OsO4 were separately placed in the bottom of short 5 mm
diameter NMR tubes (ca. 11 cm length), and a piece of col-
orless cotton was stuffed ca. 6 cm above the bottom of each
tube. Both tubes were closed with the cap and then sealed
The appropriate use of both 5% Os/CR11 and NMO in
70% aqueous acetone as well as in t-BuOH was next investi-
gated (Table 2). 5% Os/CR11 could be reduced to 0.8 mol%
without a significant decrease in the reaction efficiency in
70% aqueous acetone (Table 2, entries 1–3), while the reac-
tion became markedly suppressed by the reduction to 0.5
mol% (Table 2, entry 4). Furthermore, the use of NMO could
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 700–704

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Y. Monguchi et al.
Letter
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Table 3 5% Os/CR11-Catalyzed Oxidation of Alkenes
5% Os/CR11 (1 mol%)
NMO (1.1 equiv)
alkene
diol
70% aq acetone (0.5 mL), r.t.
(0.25 mmol)
Entry
Alkene
Time (h)
Yield (%)a
1
2
3
5 (4)b
82 (78)b
95
Ph
Ph
5
4
85
4
3.5
100
O
5
6
7
4 (5)b
8
99 (81)b
85
Ph
Ph
Ph
Figure 1 Volatility test of the 5% Os/CR11 and 4% aq OsO4: (a) 4% aq
OsO4, 0 h; (b) 4% aq OsO4, 2 weeks; (c) 5% Os/CR11, 0 h; (d) 5%
Os/CR11, 2 weeks.
CO2Et
21
75
8
9
5.5
82
third run. Therefore, the leached osmium amount in the re-
action media of the first run was then measured by ICP-
AES. Although 71% osmium of the 5% Os/CR11 was leached
into the reaction mixture under conditions A, it was found
to be reduced to less than 1% in the case of conditions B (see
Supporting Information).28 Hence, the reaction could be
carried out in t-BuOH–H2O (2 equiv) with a low osmium
leaching or in 70% aqueous acetone using only a small
amount of 5% Os/CR11 (0.8–1 mol%), while the fresh cata-
lyst should be used in the reaction system.
Ph
5 (4)b
98 (94)b
10
6
75
86
11c
24
Ph
Ph
12c
13c
24
24
82
80
O
Table 4 Reuse Test of 5% Os/CR11
Ph
OH
conditions A or B
Ar, r.t.
14c
24
89
O
Ph
O
OH
Ph
a Isolated yield.
Yield (%)a
b Conditions: 4% aq OsO4 was used instead of 5% Os/CR11.
c Conditions: The reaction was carried out using 5 mol% of 5% Os/CR11, 1.5
equiv of NMO, and 2 equiv of H2O in t-BuOH.
Run
Conditions Ab
Conditions Bc
1
100
87
86
79
41
2 (1st reuse)
3 (2nd reuse)
36
with Teflon tape (Figure 1, a and b). The cotton in the tube
of 4% aqueous OsO4 turned dark-gray within two weeks
(Figure 1, c), while the cotton in the 5% Os/CR11 tube never
changed in color even after at least six months (Figure 1, d).
These results indicate that the 5% Os/CR11 has no volatile
nature.
a Determined by 1H NMR spectroscopy using 4-nitrotoluene as an internal
standard.
b Conditions A: 5% Os/CR11 (1 mol%), NMO (1.1 equiv), 70% aq acetone,
4 h.
c Conditions B: 5% Os/CR11 (5 mol%), NMO (1.5 equiv), H2O (2 equiv), t-BuOH,
24 h.
The reuse test of 5% Os/CR11 using allyl phenyl ether as
a substrate either in 70% aqueous acetone (Table 4, condi-
tions A) or in t-BuOH–H2O (2 equiv, conditions B) unfortu-
nately revealed that the yield of the desired diol slightly de-
creased in the second run and significantly decreased in the
In conclusion, 5% Os/CR11 was readily prepared by only
immersing the commercially available chelate resin CR11 in
the methanol solution of OsO4 at room temperature. A wide
variety of alkenes were oxidized to the corresponding diols
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 700–704

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Y. Monguchi et al.
Letter
Synlett
by the combined use of 5% Os/CR11 (0.8–5 mol%) as a cata-
lyst and NMO (1.1–1.5 equiv) as a co-oxidant in 70% aque-
ous acetone or t-BuOH–H2O (2 equiv). A disadvantage of use
of 5% Os/CR11 is leaching of osmium to the reaction media,
although the latter conditions could reduce the leaching
level to less than 1% of used osmium amount. 5% Os/CR11
could be stored in a regular screw-capped vial under air
without volatilization. The facile preparation, high catalyst
activity, and easy operation of 5% Os/CR11 together with
the general and reliable quality of CR11 would be a substi-
tute for OsO4 as a catalyst for the oxidation of alkenes.
Kantam, M. L. Chem. Commun. 2002, 586. (c) Caps, V.;
Paraskevas, I.; Tsang, S. C. Appl. Catal., A 2003, 252, 37. (d) Moen,
A. R.; Ruud, K.; Anthonsen, T. J. Mol. Catal. B: Enzym. 2008, 50,
74.
(16) Metin, Ö.; Alp, N. A.; Akbayrak, S.; Biçer, A.; Gültekin, M. S.;
Özkar, S.; Bozkaya, U. Green Chem. 2012, 14, 1488.
(17) Motorina, I.; Crudden, C. M. Org. Lett. 2001, 3, 2325.
(18) (a) Choudary, B. M.; Chowdari, N. S.; Madhi, S.; Kantam, M. L.
Angew. Chem. Int. Ed. 2001, 40, 4620. (b) Choudary, B. M.;
Chowdari, N. S.; Kantam, M.; Raghavan, K. V. J. Am. Chem. Soc.
2001, 123, 9220. (c) Choudary, B. M.; Chowdari, N. S.; Madhi, S.;
Kantam, M. L. J. Org. Chem. 2003, 68, 1736.
(19) (a) Choudary, B. M.; Jyothi, K.; Kantam, M. L.; Sreedhar, B. Adv.
Synth. Catal. 2004, 346, 45. (b) Choudary, B. M.; Jyothi, K.; Roy,
M.; Kantam, M. L.; Sreedhar, B. Adv. Synth. Catal. 2004, 346,
1471.
Acknowledgment
(20) (a) Koivula, R.; Lehto, J.; Pajo, L.; Gale, T.; Leinonen, H. Hydrome-
tallurgy 2000, 56, 93. (b) Cavaco, A.; Fernandes, S.; Quina, M. M.;
Ferreira, L. M. J. Hazard. Mater. 2007, 144, 634. (c) Cavaco, S. A.;
Fernandes, S.; Augusto, C. M.; Quina, M. J.; Gando-Ferreira, L. M.
J. Hazard. Mater. 2009, 169, 516. (d) Gando-Ferreira, L. M.;
Romao, I. S.; Quina, M. J. Chem. Eng. J. 2011, 172, 277.
(21) Homepage for DIAION of Mitsubishi Chemical Co., see
http://www.diaion.com/en/.
We appreciate the kind gift of DIAION CR11 from the Mitsubishi
Chemical Corporation.
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0034-1379990.
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
ortioInfgrmoaitn
(22) Monguchi, Y.; Nozaki, K.; Maejima, T.; Shimoda, Y.; Sawama, Y.;
Kitamura, Y.; Kitade, Y.; Sajiki, H. Green Chem. 2013, 15, 490.
(23) Preparation of 5% Os/CR11
References and Notes
To a solution of OsO4 (1.00 g, 3.93 mmol) in MeOH (600 mL) was
added DIAION CR11 (40.3 g, H2O ca. 60–65%), and the mixture
was stirred at r.t. under an Ar atmosphere for 3 d. The resulting
purple resin was collected on a filter paper, washed with MeOH
(3 × 100 mL), then dried under reduced pressure to give 5%
Os/CR11 (16.3 g). The filtrate and MeOH wash were diluted to 1
L with MeOH in a volumetric flask. The inductively coupled
plasma atomic emission spectrometry (ICP-AES) of the com-
bined filtrate and MeOH wash detected 1 mg/L of osmium
species (1 mg Os in 1 L MeOH), indicating that 746.6 mg Os was
embedded on the CR11 [3.93 mmol × 190.23 (molecular weight
of Os) – 1 mg (Os in MeOH)]. Therefore, the amount of Os on
CR11 was determined to be ca. 5 weight% osmium [746.6 (mg,
weight of Os) ÷ 16300 (mg, weight of catalyst) × 100 = 4.6%].
(24) The immobilization manner of osmium to CR11 was not charac-
terized.
(1) (a) Schröder, M. Chem. Rev. 1980, 80, 187. (b) Kolb, H. C.; Van
Nieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483.
(2) (a) Nagayama, S.; Endo, M.; Kobayashi, S. J. Org. Chem. 1998, 63,
6094. (b) Wako Pure Chemical Industries, Ltd., Code No. 153-
02081.
(3) (a) Kobayashi, S.; Ishida, T.; Akiyama, R. Org. Lett. 2001, 3, 2649.
(b) Akiyama, R.; Matsuki, N.; Nomura, H.; Yoshida, H.; Yoshida,
T.; Kobayashi, S. RSC Adv. 2012, 2, 7456. (c) Wako Pure Chemical
Industries, Ltd., Code No. 158-02411.
(4) Kobayashi, S.; Endo, M.; Nagayama, S. J. Am. Chem. Soc. 1999,
121, 11229.
(5) (a) Choudary, B. M.; Chowdari, N. S.; Jyothi, K.; Kantam, M. L.
J. Am. Chem. Soc. 2002, 124, 5341. (b) Choudary, B. M.; Jyothi,
K.; Madhi, S.; Kantam, M. L. Adv. Synth. Catal. 2003, 345, 1190.
(6) Jun, B.-H.; Kim, J.-H.; Park, J.; Kang, H.; Lee, S.-H.; Lee, Y.-S.
Synlett 2008, 2313.
(25) Water should be necessary for the hydrolysis of the intermedi-
ary osmate ester, which is supposedly obtained by the cycload-
dition reaction of osmium species with an alkene.
(7) Lohray, B. B.; Thomas, A.; Chittari, P.; Ahuja, J. R.; Dhal, P. K. Tet-
rahedron Lett. 1992, 37, 5453.
(8) Choudary, B. M.; Roy, M.; Roy, S.; Jyothi, K.; Kantam, M. L.;
Sreedhar, B.; Kumar, K. V. Adv. Synth. Catal. 2006, 348, 1734.
(9) Reddy, S. M.; Srivasulu, M.; Reddy, Y. V.; Narasimhulu, M.;
Venkateswarlu, Y. Tetrahedron Lett. 2006, 47, 5285.
(10) Lee, B. S.; Mahajan, S.; Janda, K. D. Tetrahedron Lett. 2005, 46,
4491.
(11) Declue, M. S.; Siegel, J. S. Org. Biomol. Chem. 2004, 2, 2287.
(12) Pini, D.; Petri, A.; Nardi, A.; Rosini, C.; Salvadori, P. Tetrahedron
Lett. 1991, 32, 5175.
(13) Yang, J. W.; Han, H.; Roh, H. H.; Lee, S.-g.; Song, C. E. Org. Lett.
2002, 4, 4685.
(14) Fujita, K.; Inoue, K.; Tsuchimoto, T.; Yasuda, H. Chem. Pharm.
Bull. 2012, 60, 1594.
(26) General Procedure for the 5% Os/CR11-Catalyzed Oxidation
of Alkenes in 70% Aqueous Acetone
A mixture of the alkene (250 μmol), NMO (32.2 mg, 275 μmol),
and 5% Os/CR11 (9.5 mg, 2.50 μmol) in 70% aq acetone (500 μL)
was stirred under an Ar atmosphere at r.t. After the consump-
tion of the alkene (TLC analysis), the 5% Os/CR11 was removed
by filtration, and the filtrate was concentrated in vacuo. The
residue was passed through a short silica gel column chroma-
tography to give the corresponding diol. The NMR data of the
products were identical to those in the literature, see the Sup-
porting Information.
(27) General Procedure for the 5% Os/CR11-Catalyzed Oxidation
of Alkenes in t-BuOH
(15) (a) Severeyns, A.; De Vos, D. E.; Fiermans, L.; Verpoort, F.;
Grobet, P. J.; Jacobs, P. A. Angew. Chem. Int. Ed. 2001, 40, 586.
(b) Choudary, B. M.; Chowdari, N. S.; Jyothi, K.; Kumar, N. S.;
A mixture of the alkene (250 μmol), NMO (43.9 mg, 375 μmol),
5% Os/CR11 (47.6 mg, 12.5 μmol), and H2O (9.0 μL, 500 μmol) in
t-BuOH (500 μL) was stirred under an Ar atmosphere at r.t. After
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 700–704

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Y. Monguchi et al.
Letter
Synlett
24 h, the 5% Os/CR11 was removed by filtration, and the filtrate
was concentrated in vacuo. The residue was passed through a
short silica gel column chromatography to give the correspond-
ing diol.
(28) It is not clear why satisfactory reuse of 5% Os/CR11 was not
achieved even under conditions B where only a small amount of
osmium was leached out from the catalyst, although the
decrease of each run in the catalyst activity was lower than that
under conditions A.
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