Angewandte
Chemie
Table 2: Kinetic resolutions with the CoIII-4a-OAc Catalyst.
Entry Epoxide
Loading Conditions[a] Isolated epoxide
[5] a) D. B. Berkowitz, W. Shen, G.
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2004, 15, 2845; b) D. B. Berkowitz,
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1673; Angew. Chem. Int. Ed. 2002,
41, 1603.
Isolated diol
[mol%]
(yield [%], ee [%], E (yield [%], ee [%], E
value)
value)
1
1
A
70,33 ( S),11
26,72 ( R),[b]
8
2
3
1
4
A
B
44, 92 (S), 20
59, 55 (S), 16
56, 72 (R),[c]19
39, 80 (R),[d] 15
[6] For other screens with enzymes,
see: a) C. M. Sprout, C. T. Seto,
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Seto, J. Am. Chem. Soc. 2001, 123,
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Eur. J. 1998, 4, 2324; e) A. Ham-
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Buetikofer, B. Witholt, Angew.
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g) F. Badalassi, G. Klein, P. Crotti,
J.-L. Reymond, Eur. J. Org. Chem.
2004, 2557; h) G. Klein, J.-L. Rey-
mond, Helv. Chim. Acta 1999, 82,
400.
4
5
2
B
59,53 ( S),13
37,75 ( R),[d] 11
55, 72 (S),[e,f] 17
2
B
45, 93 (R),[e] 25
6
7
1
B
B
82,17 ( S),9
18,80 ( R),[f] 11
37,46 ( S),[e,h] 3.5
10
62,28 ( R),[g] 3.5
[a],[b] as described in Table 1. [c] Assigned by comparison of optical rotation with that of the known
R diol.[25] [d]–[f] See Table 1,footnotes [c]–[e],Table 1. [g] The sign of the optical rotation was found to
differ with that reported (the S epoxide is said to be levorotatory[24]),however,the R epoxide was found to
be levorotatory here). To confirm the absolute stereochemistry,the R epoxide was synthesized
independently from (S)-glycidol. [h] See Table 1,footnote [g],
[7] Using antibodies: a) H. Matsushita,
N. Yamamoto, M. M. Meijler, P.
Wirsching, R. A. Lerner, M. Mat-
sushita, K. D. Janda, Mol. BioSyst.
2005, 1, 303; b) M. Matsushita, K.
Yoshida, N. Yamamoto, P. Wirsch-
fold will likely find application well beyond the HKR
chemistry reported herein.
ing, R. A. Lerner, K. D. Janda, Angew. Chem. 2003, 115, 6166;
Angew. Chem. Int. Ed. 2003, 42, 5984; c) F. Taran, C. Gauchet, B.
Mohar, S. Meunier, A. Valleix, P. Y. Renard, C. Creminon, J.
Grassi, A. Wagner, C. Mioskowski, Angew. Chem. 2002, 114,
132; Angew. Chem. Int. Ed. 2002, 41, 124.
Received: March 23, 2007
Published online: August 14, 2007
[8] Use of aptamers: M. Michaud, E. Jourdan, A. Villet, A. Ravel,
C. Grosset, E. Peyrin, J. Am. Chem. Soc. 2003, 125, 8672.
[9] Use of synthetic molecular sensors: a) L. Zhu, S. H. Shabbir,
E. V. Anslyn, Chem. Eur. J. 2006, 12, 99; b) Z.-B. Li, J. Lin, L. Pu,
Angew. Chem. 2005, 117, 1718; Angew. Chem. Int. Ed. 2005, 44,
1690; c) S. J. Lee, W. Lin, J. Am. Chem. Soc. 2002, 124, 4554.
[10] a) D. L. Schoenfeld, U. T. Bornscheuer, Anal. Chem. 2004, 76,
1184; b) K. Mikami, R. Angelaud, K. Ding, A. Ishii, A. Tanaka,
N. Sawada, K. Kudo, M. Senda, Chem. Eur. J. 2001, 7, 730.
[11] R. Eelkema, R. A. van Delden, B. L. Feringa, Angew. Chem.
2004, 116, 5123; Angew. Chem. Int. Ed. 2004, 43, 5013.
[12] M. T. Reetz, M. H. Becker, K. M. Kuhling, A. Holzwarth,
Angew. Chem. 1998, 110, 2792; Angew. Chem. Int. Ed. 1998,
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[13] a) C. Markert, A. Pfaltz, Angew. Chem. 2004, 116, 2552; Angew.
Chem. Int. Ed. 2004, 43, 2498; b) M. T. Reetz, M. H. Becker, H.-
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Chem. Int. Ed. 1999, 38, 1758.
[14] a) M. T. Reetz, P. Tielmann, A. Eipper, A. Ross, G. Schlotter-
beck, Chem. Commun. 2004, 1366; b) M. A. Evans, J. P. Morken,
J. Am. Chem. Soc. 2002, 124, 9020.
Keywords: asymmetric catalysis · cobalt ·
combinatorial chemistry · enantioselectivity ·
UV/Vis spectroscopy
.
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[2] For reviews on combicatalysis, see: a) M. T. Reetz, Compr.
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[15] P. Tielmann, M. Boese, M. Luft, M. T. Reetz, Chem. Eur. J. 2003,
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