K. Mikami et al.
FULL PAPER
Table 5. Linear dependency of e factor and concentration (c) for (S)-3-
octanol (2).
Org. Chem. 1992, 57, 3264; c) K. Ishihara, H. Kurihara, M. Matsumoto,
H. Yamamoto, J. Am. Chem. Soc. 1998, 120, 6920.
[8] a) K. Maruoka, T. Itoh, T. Shirasaka, H. J. Yamamoto, Am. Chem. Soc.
1988, 110, 310; b) J. Bao, W. D. Wulff, A. L. Rheingold, J. Am. Chem.
Soc. 1993, 115, 3814; c) D. P. Heller, D. R. Goldberg, W. D. Wulff, J.
Am. Chem. Soc. 1997, 119, 10551; d) A. Graven, M. Johannsen, K. A.
Jorgensen, Chem. Commun. 1996, 2373.
1
c [mgmL
]
e factor
3
3
3
3
3
50
15
10
5
1.82381 Â 10
1.80138 Â 10
1.80390 Â 10
1.79748 Â 10
1.79862 Â 10
[9] a) M. T. Reetz, S. H. Kyung, C. Bolm, T. Zierke, Chem. Ind. (London)
1986, 824; b) D. Seebach, A. K. Beck, R. Imwinkelried, S. Roggo, A.
Wonnacott, Helv. Chim. Acta 1987, 70, 954; c) K. Mikami, M. Terada,
T. Nakai, J. Am. Chem. Soc. 1989, 111, 1940; d) K. Mikami, M. Terada,
T. Nakai, J. Am. Chem. Soc. 1990, 112, 3949; e) K. Mikami, M. Terada,
S. Narisawa, T. Nakai, Synlett 1992, 255; f) K. Mikami, M. Terada, S.
Narisawa, T. Nakai, Org. Synth. 1992, 71, 14; g) A. Ketter, G. Glahsl,
R. Herrmann, J. Chem. Res. 1990, 2118; h) T. Mukaiyama, A.
Inubushi, S. Suda, R. Hara, S. Kobayashi, Chem. Lett. 1990, 1015;
i) A. L. Costa, M. G. Piazza, E. Tagliavini, C. Trombini, A. J. Umani-
Ronchi, J. Am. Chem. Soc. 1993, 115, 7001; j) G. E. Keck, K. H.
Tarbet, L. S. Geraci, J. Am. Chem. Soc. 1993, 115, 8467; k) K.
Maruoka, N. Murase, H. Yamamoto, J. Org. Chem. 1993, 58, 2938;
l) D. R. Gauthier, Jr., E. M. Carreira, Angew. Chem. 1996, 108, 2521;
Angew. Chem. Int. Ed. Engl. 1996, 35, 2363; m) S. Weigand, R.
Brückner, Chem. Eur. J. 1996, 2, 1077; n) C.-M. Yu, H.-S. Choi, W.-H.
Jung, S.-S. Lee, Tetrahedron Lett. 1996, 37, 7095; o) S. Yamago, M.
Furukawa, A. Azuma, J. Yoshida, Tetrahedron Lett. 1998, 39, 3783.
[10] a) S. Casolari, P. G. Cozzi, P. Orioli, E. Tagliavini, A. Umani-Ronchi,
Chem. Commun. 1997, 2123; b) S. Kobayashi, H. Ishitani, M. Ueno, J.
Am. Chem. Soc. 1998, 120, 431; c) S. Kobayashi, S. Komiyama, H.
Ishitani, Angew. Chem. 1998, 110, 1026; Angew. Chem. Int. Ed. 1998,
37, 979; d) T. Volk, T. Korenaga, S. Matsukawa, M. Terada, K. Mikami,
Chirality, 1998, 10, 717.
1
Table 6. Determination of % ee of 1 by g and e factors.
ee [%] by
g factor
ee [%] by
e factor
96.0
64.6
25.4
0
96.0
64.1
25.6
0
Conclusion
In summary, we have successfully developed new strategies
for super high-throughput screening[26, 27] of chiral ligands and
activators by employment of the combinatorial (CC) factory
and HPLC-CD/UV or -OR/RIU systems. These SHTS
techniques combined with our ªasymmetric activationº con-
cept provides a powerful methodology for finding the best
activated catalyst. We have demonstrated a reliable SHTS for
enantiomeric excesses (ees) in asymmetric catalysis through
asymmetric activation.
[11] a) S. Kobayashi, H. Ishitani, J. Am. Chem. Soc. 1994, 116, 4083; b) S.
Kobayashi, Synlett 1994, 689; c) K. Mikami, O. Kotera, Y. Motoyama,
H. Sakaguchi, Synlett 1995, 975; d) H. Kitajima, T. Katsuki, Synlett
1997, 568; e) I. E. Marko, G. R. Evans, P. Seres, I. Chelle, Z. Janousek,
Pure Appl. Chem. 1996, 68, 113; f) M. Shibasaki, H. Sasai, T. Arai,
Angew. Chem. 1997, 109, 1290; Angew. Chem. Int. Ed. Engl. 1997, 36,
1236, and references therein.
[12] K. R. K. Prasad, N. N. Joshi, Tetrahedron Asymmetry 1996, 7, 1957.
[13] a) H. Kitajima, K. Ito, T. Katsuki, Chem. Lett. 1996, 343; H. Kitajima,
K. Ito, Y. Aoki, T. Katsuki, Bull. Chem. Soc. Jpn. 1997, 70, 207; b) Q. S.
Hu, W. S. Huang, D. Vitharana, X. F. Zhang, L. Pu, J. Am. Chem. Soc.
1997, 119, 12454; c) W. S. Huang, Q. S. Hu, L. Pu, J. Org. Chem. 1998,
63, 1364; d) Q. S. Hu, W. S. Huang, L. Pu, J. Org. Chem. 1998, 63, 2798;
e) W. S. Huang, L. Pu, J. Org. Chem. 1999, 64, 4222.
[14] S. E. Denmark, S. P. OꢁConnor, S. R. Wilson, Angew. Chem. 1998, 110,
1162; Angew. Chem. Int. Ed. 1998, 37, 1149.
[15] P. G. Cozzi, A. Papa, A. Umani-Ronchi, Tetrahedron Lett. 1996, 37,
4613.
[16] Special issues on combinatorial library: a) Acc. Chem. Res. 1996, 29,
No. 3; b) Chem. Eng. News 1996, 74, No. 7; reviews: c) F. Balkenhohl,
C. B. Hunnefeld, A. Lansky, C. Zechel, Angew. Chem. 1996, 108, 2436;
Angew. Chem. Int. Ed. Engl. 1996, 35, 2288; d) C. Gennari, H. P.
Nestler, U. Piarulli, B. Salom, Liebigs Ann. 1997, 637; e) Combinato-
rial Chemistry: Synthesis and Application (Eds.: S. R. Wilson, A. W.
Czarink), Wiley, New York, 1997; f) Combinatorial Chemistry and
Technology (Eds.: S. Miertus, G. Fassina), Marcel Dekker, New York,
1997.
[1] a) R. E. Gawley, J. Aube, Principles of Asymmetric Synthesis, Perga-
mon, London, 1996; b) Advances in Catalytic Processes, Vol. 1 (Ed.:
M. P. Doyle), JAI, London, 1995; c) R. Noyori, Asymmetric Catalysis
in Organic Synthesis, Wiley, New York, 1994; d) H. Brunner, W.
Zettlmeier, Handbook of Enantioselective Catalysis, VCH, Weiheim,
1993; e) Catalytic Asymmetric Synthesis (Ed.: I. Ojima), VCH, New
York, 1993; f) H. B. Kagan, Comprehensive Organic Chemistry, Vol. 8,
Pergamon, Oxford, 1992; g) Asymmetric Catalysis (Ed.: B. Bosnich),
Martinus Nijhoff, Dordrecht, 1986.
[2] a) D. J. Berrisford, C. Bolm, K. B. Sharpless, Angew. Chem. 1995, 107,
1159; Angew. Chem. Int. Ed. Engl. 1995, 34, 1059; b) E. N. Jacobsen, I.
Marko, M. B. France, J. S. Svendsen, K. B. Sharpless, J. Am. Chem.
Soc. 1989, 111, 737.
[3] a) R. D. Rieke, Top. Curr. Chem. 1975, 59, 1; b) E. Erdik, Tetrahedron
1987, 43, 2203; c) P. Knochel, R. D. Singer, Chem. Rev. 1993, 93, 2117;
d) M. Nakamura, E. Nakamura, J. Synth. Org. Chem. Jpn. 1998, 56,
632; e) K. Takai, T. Kakiuchi, K. Uchimoto, J. Org. Chem. 1994, 59,
2668; f) K. Takai, T. Kakiuchi, K. Uchimoto, J. Org. Chem. 1994, 59,
2671.
[17] a) K. Burgess, H.-J. Lim, A. M. Porte, G. A. Sulikowski, Angew. Chem.
1996, 108, 192; Angew. Chem. Int. Ed. Engl. 1996, 35, 220; b) A. M.
Porte, J. Reibenspies, K. Burgess, J. Am. Chem. Soc. 1998, 120, 9180;
c) B. M. Cole, K. D. Shimizu, C. A. Krueger, J. P. A. Harrity, M. L.
Snapper, A. H. Hoveyda, Angew. Chem. 1996, 108, 1776; Angew.
Chem. Int. Ed. Engl. 1996, 35, 1668; d) K. D. Shimizu, B. M. Cole,
C. A. Krueger, K. W. Kuntz, M. L. Snapper, A. H. Hoveyda, Angew.
Chem. 1997, 109, 1781; Angew. Chem. Int. Ed. Engl. 1997, 36, 1703;
e) C. A. Krueger, K. W. Kuntz, C. D. Dzierba, W. G. Wirschun, J. D.
Gleason, M. L. Snapper, A. H. Hoveyda, J. Am. Chem. Soc. 1999, 121,
4284; f) M. S. Sigman, E. N. Jacobsen, J. Am. Chem. Soc. 1998, 120,
4901; g) M. B. Francis, E. N. Jacobsen, Angew. Chem. 1999, 111, 987;
Angew. Chem. Int. Ed. 1999, 38, 937; h) G. A. Liu, J. Ellman, J. Org.
Chem. 1995, 60, 7712.
[4] a) K. Soai, S. Niwa, Chem. Rev. 1992, 92, 833; b) R. Noyori, M.
Kitamura, Angew. Chem. 1991, 103, 34; Angew. Chem. Int. Ed. Engl.
1991, 30, 49.
[5] a) N. Oguni, T. Omi, Tetrahedron Lett. 1984, 25, 2823; for leading
references: b) C. Bolm, K. Muniz, J. P. Hildebrand, Org. Lett. 1999, 1,
491; c) M. Kitamura, H. Oka, R. Noyori, Tetrahedron 1999, 55, 3605;
d) P. I. Dosa, G. C. Fu, J. Am. Chem. Soc. 1998, 120, 445.
[6] Reviews: a) J. K. Whitesell, Chem. Rev. 1989, 89, 1581; b) C. Rosini, L.
Franzini, A. Raffaelli, P. Salvadori, Synthesis 1992, 503; c) K. Mikami,
Y. Motoyama, Encyclopedia of Reagents for Organic Synthesis. Vol. 1
(Ed.: L. A. Paquette), Wiley, Chichester, 1995, p. 395; d) L. Pu, Chem.
Rev. 1998, 98, 2405.
[7] a) D. Kaufmann, R. Boese, Angew. Chem. 1990, 102, 568; Angew.
Chem. Int. Ed. Engl. 1990, 29, 545; b) K. Hattori, H. Yamamoto, J.
736
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