LETTER
Polystyrene-sg-imidazolium Resin-Supported Osmium Complex
2315
Table 3 Reusability Test of PS-sg-IM Os19
(5) (a) Nagayama, S.; Endo, M.; Kobayashi, S. J. Org. Chem.
1998, 63, 6094. (b) Kobayashi, S.; Endo, M.; Nagayama, S.
J. Am. Chem. Soc. 1999, 121, 11229. (c) Kobayashi, S.;
Ishida, T.; Akiyama, R. Org. Lett. 2001, 3, 2649. (d)Ishida,
T.; Akiyama, R.; Kobayashi, S. Adv. Synth. Catal. 2003,
345, 576. (e) Ishida, T.; Akiyama, R.; Kobayashi, S. Adv.
Synth. Catal. 2005, 347, 1189. (f) Ley, S. V.; Ramarao, C.;
Lee, A.-L.; Østergaard, N.; Smith, S. C.; Shirley, I. M. Org.
Lett. 2003, 5, 185. (g) Reddy, S. M.; Srinivasulu, M.;
Reddy, Y. V.; Narashimhulu, M.; Venkateswarlu, Y.
Tetrahedron Lett. 2006, 47, 5285.
(6) (a) Jiang, R.; Kuang, Y.; Sun, X.; Zhang, S. Acta Chim. Slov.
2005, 52, 467. (b) Choudary, B. M.; Chowdari, N. S.;
Kantam, M. L.; Raghavan, K. V. J. Am. Chem. Soc. 2001,
123, 9220. (c) Choudary, B. M.; Chowdari, N. S.; Jyothi, K.;
Kantam, M. L. J. Am. Chem. Soc. 2002, 124, 5341.
(d) Choudary, B. M.; Jyothi, K.; Madhi, S.; Kantam, M. L.
Adv. Synth. Catal. 2003, 345, 1190.
HO
PS-sg-IM Os (1 mol%)
NMO (1.3 equiv)
OH
H2O–acetone (1:3)
25 °C
1 mmol
Entry
Time (h)
Isolated yield (%)
First use
Second use
Third use
2
4
6
94
93
93
tected from the filtrates after each runs (9%, 26% and
16%, by ICP-AES analysis of filtrate), thus prolonged re-
action times were required in successive experiments.
Considering that we only used 1 mol% osmium as a cata-
lyst, our results are comparable with those reported by
others.
(7) Lee, B. S.; Mahajan, S.; Janda, K. D. Tetrahedron Lett.
2005, 46, 4491.
(8) (a) Tang, W.-J.; Yang, N.-F.; Yi, B.; Deng, G.-J.; Hunag,
Y.-Y.; Fan, Q.-H. Chem. Commun. 2004, 1378. (b) Huang,
Y.; Meng, W.-D.; Qing, F.-L. Tetrahedron Lett. 2004, 45,
1965. (c) Yang, J. W.; Han, H.; Roh, E. J.; Lee, S.; Song,
C. E. Org. Lett. 2002, 4, 4685.
In conclusion, we successfully prepared PS-sg-IM Os, in
which the catalytic active sites are located only on the sur-
face of the polymer. This osmium complex gave excellent
catalytic activity in DH of olefins. After completion of the
reaction, the catalyst was recovered by simple filtration
and could be reused three times, although gradual loss of
activity was observed. To overcome this leaching prob-
lem, the preparation of Os complex on different kinds of
polymer matrixes and its use in the osmium-catalyzed di-
hydroxylation of olefins are now in progress and will be
reported in due course.
(9) Kobayashia, S.; Sugiura, M. Adv. Synth. Catal. 2006, 348,
1496.
(10) (a) Yao, Q. Org. Lett. 2002, 4, 2197. (b) Yanada, R.;
Takemoto, Y. Tetrahedron Lett. 2002, 43, 6849.
(c) Branco, L. C.; Afonso, C. A. M. Chem. Commun. 2002,
3036. (d) Song, C. E.; Jung, D.; Roh, E. J.; Lee, S.; Chi,
D. Y. Chem. Commun. 2002, 3038. (e) Branco, L. C.;
Afonso, C. A. M. J. Org. Chem. 2004, 69, 4381. (f) Liu, Q.;
Zhang, Z.; van Rantwijk, F.; Sheldon, R. A. J. Mol. Catal. A:
Chem. 2004, 224, 213. (g) Jiang, R.; Kuang, Y.; Sun, X.;
Zhang, S. Tetrahedron: Asymmetry 2004, 15, 743.
(h) Branco, L. C.; Serbanovic, A.; da Ponte, M. N.; Afonso,
C. A. M. Chem. Commun. 2005, 107. (i) Serbanovic, A.;
Branco, L. C.; da Ponte, M. N.; Afonso, C. A. M.
J. Organomet. Chem. 2005, 690, 3600. (j) Closson, A.;
Johansson, M.; Bäckvall, J.-E. Chem. Commun. 2004, 1494.
(k) Johansson, M.; Lindøn, A. A.; Bäckvall, J.-E.
J. Organomet. Chem. 2005, 690, 3614. (l) Dioos, B. M. L.;
Vankelecom, I. F. J.; Jacobsa, P. A. Adv. Synth. Catal. 2006,
348, 1413.
Acknowledgment
This work was supported by the Nano-Systems Institute-National
Core Research Center (NSI-NCRC) program, by the Nano-Bioelec-
tronics and Systems Research Center of KOSEF, Korea, and a grant
of the Korea Health 21 R&D Project, Ministry of Health & Welfare,
Republic of Korea (A050432) and the Brain Korea 21 Program sup-
ported by the Ministry of Education and Human Resources De-
velopment.
(11) Welton, T. Chem. Rev. 1999, 99, 2071.
(12) Vanrheenen, V.; Kelly, R. C.; Cha, D. Y. Tetrahedron Lett.
1976, 17, 1973.
References and Notes
(13) (a) Jang, H. S.; Chung, W. J.; Lee, Y. S. Tetrahedron Lett.
2007, 48, 3731. (b) Yi, S. S.; Lee, D. H.; Sin, E.; Lee, Y. S.
Tetrahedron Lett. 2007, 48, 6771.
(1) New address: J. H. Kim, Department of Chemical
Engineering, Massachusetts Institute of Technology,
Cambridge, MA 02139, USA.
(2) (a) Johnson, R. A.; Sharpless, K. B. In Catalytic Asymmetric
Synthesis, 2nd ed.; Ojima, I., Ed.; VCH: Weinheim, 2000,
357. (b) Tori, S.; Liu, P.; Bhuvaneswari, N.; Amatore, C.;
Jutand, A. J. Org. Chem. 1996, 61, 3055. (c) Lohray, B. B.;
Nandanan, E.; Bhushan, V. Tetrahedron: Asymmetry 1996,
7, 645.
(3) Leadbeater, N. E.; Marco, M. Chem. Rev. 2002, 102, 3217.
(4) Cornils, B.; Herrmann, W. A. Applied Homogeneous
Catalysis with Organometallic Compounds; Wiley-VCH:
Weinheim, 1996, Chap. 3.1.
(14) (a) Byun, J. W.; Lee, Y. S. Tetrahedron Lett. 2004, 45,
1837. (b) Jun, B. H.; Kim, J. H.; Park, H.; Kim, J.; Yu, K. N.;
Lee, S. M.; Choi, H. J.; Kwak, S. Y.; Kim, Y.; Jeong, D. H.;
Cho, M.; Lee, Y. S. J. Comb. Chem. 2007, 9, 237.
(15) (a) Kim, J. H.; Jun, B. H.; Byun, J. W.; Lee, Y. S.
Tetrahedron Lett. 2004, 45, 5827. (b) Kim, J. H.; Kim, J.
W.; Shokouhimehr, M.; Lee, Y. S. J. Org. Chem. 2005, 70,
6714.
(16) (a) Shokouhimehr, M.; Kim, J. H.; Lee, Y. S. Synlett 2006,
618. (b) Kim, J. W.; Kim, J. H.; Lee, D. H.; Lee, Y. S.
Tetrahedron Lett. 2006, 47, 4745. (c) Kim, J. H.; Lee, D. H.;
Jun, B. H.; Lee, Y. S. Tetrahedron Lett. 2007, 48, 7079.
(d) Lee, D. H.; Kim, J. H.; Jun, B. H.; Kang, H.; Park, J.; Lee,
Y. S. Org. Lett. 2008, 8, 1609.
Synlett 2008, No. 15, 2313–2316 © Thieme Stuttgart · New York