3242
Y. Arakawa et al. / Tetrahedron Letters 47 (2006) 3239–3243
Encouraged by the results mentioned above, asymmetric
transfer hydrogenation of various ketones by using the
catalyst prepared from (R,R)-6 were investigated (Table
Ed.; CRC Press: Boca Raton, 1996; Vol. 10, pp 8078–
087; (c) Dickerson, T. J.; Read, N. N.; Janda, K. D.
Chem. Rev. 2002, 102, 3325–3344; (d) Chan, A. S.; Fan,
Q.-H.; Li, Y.-M. Chem. Rev. 2002, 102, 3385–3466; (e)
Leadbeater, N. E.; Marco, M. Chem. Rev. 2002, 102,
8
2
1
). Propiophenone (8b), p-chloroacetophenone (8c), and
-acetonaphthone (8d) are chosen as substrate, which
0
3
217–3274.
. Uozumi, Y.; Kobayashi, Y. Heterocycles 2003, 59, 71–
4.
are converted into the corresponding optically active
secondary alcohols with excellent enantioselectivities,
4
5
7
9
6% ee (entry 2), 99% ee (entry 3), 97% ee (entry 4),
. Uozumi, Y.; Danjo, H.; Hayashi, T. Tetrahedron Lett.
1998, 39, 8303–8306.
6. For studies on polymer-supported chiral catalysts for
asymmetric reaction in water, see: (a) Ishida, T.; Akiyama,
R.; Kobayashi, S. Adv. Synth. Catal. 2005, 347, 1189–
respectively. As can be seen in Table 2, the enantioselec-
tivities obtained in these reactions using polymeric cata-
9
a
lyst are superior to that in the model reaction using
monomeric one. To our knowledge, there have been
only a few reports of polymeric chiral catalysts that
exhibited higher enantioselectivity than that obtained
1
2
192; (b) Nakai, Y.; Uozumi, Y. Org. Lett. 2005, 7, 291–
93; (c) Schlatter, A.; Kundu, M. K.; Woggon, W. D.
1
4
Angew. Chem., Int. Ed. 2004, 43, 6731–6734; (d) Liu, P.
N.; Deng, J. G.; Tu, Y. Q.; Wang, S. H. Chem. Commun.
from their low molecular weight counterparts.
2
004, 2070–2071; (e) Otomaru, Y.; Senda, T.; Hayashi, T.
In summary, we have successfully synthesized new poly-
mer-supported chiral 1,2-diamine monosulfonamides
containing sulfonated pendant group. This is the first
example of the use of sulfonated polymer-support for
asymmetric catalyst in water. Chiral catalyst prepared
from the new polymer-support is more effective for
asymmetric transfer hydrogenation of aromatic ketones
in water compared to that prepared from conventional
polystyrene-support. We have also found that polysty-
rene-support containing quaternary ammonium salt of
the pendant sulfonate was very important as a polymeric
catalyst used in aqueous media, which increased not
only the reactivity but also the enantioselectivity in this
reaction. We are currently using this type of polymer-
support for other organic reactions in aqueous media.
Org. Lett. 2004, 6, 3357–3359; (f) Uozumi, Y.; Tanaka, H.;
Shibatomi, K. Org. Lett. 2004, 6, 281–283; (g) Li, X. G.;
Wu, X. F.; Chen, W. P.; Hancock, F. E.; King, F.; Xiao, J.
Org. Lett. 2004, 6, 3321–3324; (h) Benaglia, M.; Cinquini,
M.; Cozzi, F.; Celentano, G. Org. Biomol. Chem. 2004, 2,
3
401–3407; (i) Zarka, M. T.; Nuyken, O.; Weberskirch, R.
Chem. Eur. J. 2003, 9, 3228–3234; (j) Uozumi, Y.;
Shibatomi, K. J. Am. Chem. Soc. 2001, 123, 2919–2920;
(
k) Liu, P. N.; Gu, P.; Deng, J. G.; Tu, Y. Q.; Ma, Y. P.
Eur. J. Org. Chem. 2005, 3221–3227.
. (a) Malmstrom, T.; Andersson, C. Chem. Commun. 1996,
7
1
135–1136; (b) Malmstrom, T.; Andersson, C. J. Mol.
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8. For example, the standard ligand of aqueous biphase
0
00
catalysis is 3,3 ,3 -phosphinidynetris[benzenesulfonic
acid], trisodium salt TPPTS. Cornils, B.; Kuntz, E. G. J.
Organomet. Chem. 1995, 502, 177–186.
9
. (a) Wu, X.; Li, X.; Hems, W.; King, F.; Xiao, J. Org.
Biomol. Chem. 2004, 2, 1818–1821; (b) Thorpe, T.;
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S.; Muxworthy, J. P.; Williams, J. M. J. Tetrahedron Lett.
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M.; Crosby, J.; Fitzjohn, S.; Muxworthy, J. P.; Thorpe, T.;
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Acknowledgment
This work was partially supported by a Grant-in-Aid for
Scientific Research from the Ministry of Education,
Science, Sports and Culture of Japan.
(
d) Ma, Y.; Liu, H.; Chen, L.; Cui, X.; Zhu, J.; Deng, J.
Org. Lett. 2003, 5, 2103–2106; (e) Rhyoo, H. Y.; Park, H.;
Chung, Y. K. Chem. Commun. 2001, 2064–2065; (f) Wang,
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Chem. 2005, 70, 9424–9429.
References and notes
1
. Aqueous Phase Organometallic Catalysis, 2nd ed.; Cornils,
B., Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, 2004.
. Review on asymmetric reaction in aqueous media, see: (a)
Manabe, K.; Kobayashi, S. Chem. Eur. J. 2002, 8, 4095–
10. For examples of asymmetric transfer hydrogenation of
ketones in organic solvent by using polymer-supported
chiral catalyst, see: (a) Li, X.; Chen, W.; Hems, W.; King,
F.; Xiao, J. Tetrahedron Lett. 2004, 45, 951–953; (b) Liu,
P. N.; Gu, P. M.; Wang, F.; Tu, Y. Q. Org. Lett. 2004, 6,
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1258.
2
4101; (b) Sinou, D. Adv. Synth. Catal. 2002, 344, 221–237;
(
c) Lindstr o¨ m, U. M. Chem. Rev. 2002, 102, 2751–2772;
Typical examples of asymmetric reaction in aqueous
media, see: (d) Wang, F.; Liu, H.; Cun, L.; Zhu, J.; Deng,
J.; Jiang, Y. J. Org. Chem. 2005, 70, 9424–9429 (asym-
metric transfer hydrogenation); (e) Azoulay, S.; Manabe,
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metric ring opening of meso-epoxide); (f) Scarso, A.;
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11. Hashiguchi, S.; Fujii, A.; Takehara, J.; Ikariya, T.;
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12. Polymerization condition: Chiral monomer (R,R)-1
(0.2 mmol), quaternary ammonium salt of p-styrenesulfo-
nate (1.6 mmol), and divinlybenzene (0.2 mmol) were
weighed into an ampoule with AIBN (2 mol % to the
total monomer) and DMF. The ampoule was sealed after
three cycles of freeze–thaw under liquid nitrogen. Copo-
lymerization was carried out at 60 °C for 15 h to give
(
asymmetric sulfoxidation of thioether); (g) Dickins, R. S.;
Gaillard, S.; Hughes, S. P.; Badari, A. Chirality 2005, 17,
57–363 (asymmetric NaBH reduction); (h) Hamada, T.;
3
4
Manabe, K.; Kobayashi, S. J. Am. Chem. Soc. 2004, 126,
768–7769 (asymmetric Mannich-type reaction).
7
1
3
. Reviews on asymmetric reaction using polymer-supported
catalyst, see: (a) Itsuno, S.; Haraguchi, N.; Arakawa, Y.
Recent Res. Dev. Org. Chem. 2005, 9, 27–47; (b) Itsuno, S..
In Polymeric Materials Encyclopedia; Salamone, J. C.,
(R,R)-7 in 94% yield. Gel phase H NMR (400 MHz,
DMSO-d
1.1 (br, CH
CH Ph), 6.4–7.1, 7.1–7.9 (br, Ar–H).
6
) of (R,R)-7 showed peaks at d = 0.8 (br, CH
3
),
2
), 1.6 (br, CH ), 3.1 (br, CH N) 4.5 (br,
2
2
2