On the stereoselectivity in bisdihydroxylation of 1,5-cyclooctadiene with osmium tetroxide

Article abstract of DOI:10.1081/SCC-100104460

In the bisdihydroxylation of 1,5-cyclooctadiene with OsO₄, use of a stoichiometric amount of OsO₄ yielded a 1:1 mixture of syn- and anti-isomers, while use of a catalytic amount of OsO₄ gave only syn-(1R*,2S*,5R*,6S*)-cyclooctane-1,2,5,6-tetrol. This syn-selectivity was attributed to the favorable formation of an intramolecular osmium(VI) bisglycolate ester in the catalytic reaction.

Full text of DOI:10.1081/SCC-100104460

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ON THE STEREOSELECTIVITY IN BISDIHYDROXYLATION
OF 1,5-CYCLOOCTADIENE WITH OSMIUM TETROXIDE
Kentaro Kawazoe a , Yoshio Furusho a , Saburo Nakanishi a & Toshikazu Takata a
a Department of Applied Chemistry , College of Engineering , Osaka Prefecture
University, 1-1, Gakuen-cho, Sakai, Osaka, 599-8531, Japan
Published online: 09 Nov 2006.
To cite this article: Kentaro Kawazoe , Yoshio Furusho , Saburo Nakanishi & Toshikazu Takata (2001) ON THE
STEREOSELECTIVITY IN BISDIHYDROXYLATION OF 1,5-CYCLOOCTADIENE WITH OSMIUM TETROXIDE, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:14, 2107-2112,
DOI: 10.1081/SCC-100104460
To link to this article: http://dx.doi.org/10.1081/SCC-100104460
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SYNTHETIC COMMUNICATIONS, 31(14), 2107–2112 (2001)
ON THE STEREOSELECTIVITY IN
BISDIHYDROXYLATION OF
1,5-CYCLOOCTADIENE WITH
OSMIUM TETROXIDE
Kentaro Kawazoe, Yoshio Furusho, Saburo Nakanishi,
and Toshikazu Takata*
Department of Applied Chemistry, College of Engineering,
Osaka Prefecture University, 1-1, Gakuen-cho,
Sakai, Osaka 599-8531, Japan
ABSTRACT
In the bisdihydroxylation of 1,5-cyclooctadiene with OsO4,
use of a stoichiometric amount of OsO4 yielded a 1:1 mixture
of syn- and anti-isomers, while use of a catalytic amount of
OsO4 gave only syn-(1R*,2S*,5R*,6S*)-cyclooctane-1,2,5,6-
tetrol. This syn-selectivity was attributed to the favorable for-
mation of an intramolecular osmium(VI) bisglycolate ester in
the catalytic reaction.
For years, chemists have made efforts to develop osmium-catalyzed
dihydroxylation which is utilized as a powerful tool to build 1,2-diols.1
At the same time, the reaction mechanism leading to the first stable pro-
duct, a cyclic osmate(VI) complex, is still under discussion.2 Development
* Corresponding author. Fax: þ81-722-54-9910; E-mail: takata@chem.osakafu-u.ac.jp
2107
Copyright & 2001 by Marcel Dekker, Inc.
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KAWAZOE ET AL.
of an enantioselective catalytic version of the reaction based on cinchona
alkaloids facilitated preparation of highly oxygenated molecules.3 However,
the osmium-catalyzed polydihydroxylation of polyenes has been hardly
explored due to various reasons.1 We have investigated the osmium-cata-
lyzed bisdihydroxylation of 1,5-cyclooctadiene 1 as part of our program to
utilize (1R*,2S*,5R*,6S*)-cyclooctane-1,2,5,6-tetrol syn-2 as a scaffold for
supramolecules.4 Recently, Sharpless has reported5 the bisdihydroxylation
of several dienes, including 1, by use of Narasaka’s method.6 Herein we
report the stereoselective bisdihydroxylation of 1 and the origin of the
stereoselectivity.
The bisdihydroxylation of 1 was carried out with a catalytic amount of
osmium tetroxide (1 mol%) and an equivalent of N-methylmorpholine
N-oxide (NMO) as cooxidant in aqueous media, acetone-water (1/2 (v/v),
r.t., 12 h).7 The bisdihydroxylated product was obtained in 99% yield after
chromatography and identified as syn-isomer (1R*,2S*,5R*,6S*)-2 from the
spectroscopic results.
No anti-isomer (1R*,2S*,5S*,6R*)-2 was detected. The results of this
bisdihydroxylation were similar to those of Sharpless.5 The issue of syn/anti-
stereochemistry for the tetrol had remained unresolved8 until it was deter-
mined by us4 and Sharpless.5 We established the syn-stereochemistry of the
product by X-ray crystallography (Figure 1).9
On the other hand, bisdihydroxylation of 1 under stoichiometric con-
ditions gave a 1:1 mixture of syn- and anti-2 in 89% yield. To investigate the
origin of the syn-selectivity of the catalytic system, dihydroxylation of 1 with
one mole of NMO was carried out. The reaction selectively afforded syn-2 in
49% yield and neither anti-2 nor a monodihydroxylated product was detec-
ted at all. These results indicate that the diol moiety formed first enhances
the rate of the second dihydroxylation and controls the stereoselectivity in
the bisdihydroxylation.
To confirm such possibility, dihydroxylation of three other olefins 3ꢀ5
was conducted under the catalytic conditions. The results are shown in
Table 2. Dihydroxylation of cis-5-cyclooctene-1,2-diol 38 gave syn-2 in
99% yield, whereas 1,2-O-isopropylidene-5-cyclooctene-1,2-diol 410 afforded
a 1:1 mixture of syn- and anti-diol 6 in 94% yield.11 On the other hand,

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1,5-CYCLOOCTADIENE WITH OSMIUM TETROXIDE
2109
Figure 1. The ORTEP drawing of syn-2.
Table 1. Bisdihydroxylation of 1,5-Cyclooctadiene (1)
Entry
1
OsO4/mol%
1
NMO/mol%
200
Yield/%a
97
(syn:anti ¼ 100:0)
2b
3
200
1
0
89
(syn:anti ¼ 50:50)
49
100
(syn:anti ¼ 100:0)
b
aIsolated yield. CH2Cl2 was used as solvent instead of acetone-water.
bisdihydroxylation of 1,4-cyclohexadiene 5 gave a 1:2 mixture of syn- and
anti-tetrol 7.12
Based on the results described above, we propose the reaction mechan-
ism of the catalytic bisdihydroxylation of 1,5-cyclooctadiene as illustrated in
Scheme 1.13 The key intermediate is an intramolecular osmium(VI) bisgly-
colate ester C14, which is crucial for elucidating the syn-selectivity of the
bisdihydroxylation of 1. First of all, 1 reacts with OsO4 to form a primary
osmate A. A is oxidized with NMO to give osmium(VIII) trioxoglycolate B,
which is quickly converted to bisglycolate ester C through intramolecular
cyclization. cis-5-Cyclooctene-1,2-diol 3, which might be formed via hydro-
lysis of A, smoothly reacts with OsO4 to give B. Neither A nor B is converted
to bisosmate D or E, since the concentration of OsO4 is very low under

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KAWAZOE ET AL.
Scheme 1. Proposed mechanism of OsO4-catalyzed bisdihydroxylation of 1,5-
cyclo-octadiene.
Table 2. Osmium-catalyzed Dihydroxylation of
Olefins (3–5)

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1,5-CYCLOOCTADIENE WITH OSMIUM TETROXIDE
2111
the catalytic conditions. If D or E were formed, the syn-selectivity should
be lowered. This is understandable from the results of the experiment using
a stoichiometric amount of OsO4. The syn/anti product distribution of
the dihydroxylation of 4 and 5 well supports our proposed mechanism,
in which the formation of the intramolecular bisglycolate ester is unambi-
guously indispensable to attain the syn-selectivity: (1) because 4 does not
have a diol moiety, intramolecular bisglycolate ester cannot be formed,
resulting in the reaction without syn-selectivity; (2) since the distance
between the two olefin moieties in the 6-membered ring of 5 is too short
to form the corresponding intramolecular bisglycolate ester, the second
dihydroxylation either takes place sluggishly or occurs after hydrolysis of
the primary osmate. The primary osmate or the diol moiety formed first acts
as steric hindrance, thus to increase anti-selectivity.
REFERENCES
1. a) Schroder, M. Chem. Rev. 1980, 80, 187. b) Singh, H.S. in Organic
Syntheses by Oxidation with Metal Compounds, ed. Mijs, W.J., de Jong,
R.H.I. Plenum Press, New York, 1986, Chap. 12.
2. Rouhi, A.M. C&EN. 1997, November 3, 23 and references cited
therein.
3. Kolb, H.C.; VanNieuwenhze, M.S.; Sharpless, K.B. Chem. Rev. 1994,
94, 2483.
4. a) Takata, T.; Kawazoe, K.; Furusho, Y.; Nakanishi, S. Abstr. 1G227
in the 72nd Annual Meeting of the Chemical Society of Japan, Tokyo,
1997. b) Kawazoe, K.; Furusho, Y.; Nakanishi, S.; Takata, T. Abstr.,
2D630 in the 74th Annual Meeting of the Chemical Society of Japan,
Kyoto, 1998.
5. Gysper, A.; Michel, D.; Nirschl, D.S.; Sharpless, K.B. J. Org. Chem.
1998, 63, 7322.
6. a) Iwasawa, N.; Kato, T.; Narasaka, K. Chem. Lett. 1988, 1721. b)
Sakurai, H.; Iwasawa, N.; Narasaka, K. Bull. Chem. Soc. Jpn. 1996,
69, 2585.
7. To a mixture of OsO4 (7 mg, 0.03 mmol), NMO (6.2 mmol), water
(2.4 mL), and acetone (1.2 mL) was added 1 (324 mg, 3.0 mmol). The
mixture was stirred at room temperature for 12 h. After addition of
sat.Na2SO3aq, the mixture was evaporated and the residue was chro-
matographed over silica gel (eluent: water-ethanol-ethyl acetate (1:2:5))
to afford syn-2 as white crystals; mp 176–178ꢁC (lit.5 171–173ꢁC); IR
(KBr): vO-H 3384 cmꢂ1; 1H NMR (270 MHz, DMSO-d6, 295 K): ꢀ 4.19

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KAWAZOE ET AL.
(4H, br s, OH), 3.57 (4H, m, CH), 1.86 (4H, m, CH2), 1.36 (86 (4H, m,
CH2)); 13C NMR (270 MHz, DMSO-d6, 295 K): ꢀ 71.9, 26.8.
8. Powell, K.A.; Hughes, A.L.; Katchian, H.; Jerauld, J.F.; Sable, H.Z.
Tetrahedron 1972, 28, 2019.
9. Crystal data for syn-2: C8H16O4, M ¼ 176.21, tetragonal, space group
I41cd(#110), a ¼ 22.520(6), b ¼ 7.030(4) A, V¼3565(2) A3, Z ¼ 16, ꢁ
calcd ¼ 1.313 g cmꢂ3, F(000) ¼ 1536.00, 2ꢂmax ¼ 55.1ꢁ, MoKꢃ (1 ¼
0.71069 A), m(MoKꢃ) ¼ 1.04 cmꢂ1; A total of 1215 reflections were col-
lected at 296 ꢃ 1 K on a Rigaku AFC5R diffractometer with graphite
monochromated Mo-Kꢃ radiation and a rotating anode generator.
The structure was solved by direct methods (SIR 92) and refined
with 768 reflections (I >3.00 ꢄ (I)) and 109 variable parameters;
GOF ¼ 1.03, R ¼ 0.052, Rw ¼ 0.054. Atomic coordinates, bond lengths
and angles, and thermal parameters have been deposited at Cambridge
Crystallographic Center (CCDC). Any request to the CCDC for this
material should quote the full literature citation and the reference
number No.9/00846B.
10. 4 was prepared from 3 and acetone by use of FeCl3 as catalyst.
11. The syn/anti isomer ratio of 6 was determined by the 1H NMR spectra.
The 1H NMR assignment was achieved by comparing with that of syn-
6 prepared independently by monoacetalization of syn-2.
12. McCasland, G.E.; Furuta, S.; Johnson, L.F.; Shooler, J.N. J. Org.
Chem. 1963, 28, 894.
13. This proposed scheme is simplified for clarity, and the most notable
omissions are the various fast equilibria involving association and dis-
sociation of the ligand with osmium complexes.
14. Sharpless reported that the formation of an osmium(VI) bisglycolate
ester was observed in osmium-catalyzed dihydroxylation of a mono-
´
olefin: Wai, J.S.M.; Marko, I.; Svendsen, J.S.; Finn, M.G.; Jacobsen,
E.N.; Sharpless, K.B. J. Am. Chem. Soc. 1989, 111, 1123.
Received in Japan July 11, 2000

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