COMMUNICATIONS
aliquot with an internal standard (cyclohexanol in phosphate buffer), and
then calibrating the measured relative area in the chromatogram with their
corresponding response factors. The reaction was monitored for 24 h.
[22] a) A. Kohen, J. P. Klinman, Acc. Chem. Res. 1998, 31, 397, and
references therein; b) J. K. Chin, J. P. Klinman, Biochemistry 2000, 39,
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[23] S. Ramaswamy, D.-H. Park, B. C. Plapp, Biochemistry, 1999, 38, 13951.
[24] Several model NADH compounds have been used with Zn2 complex
catalysis for catalytic hydride transfer to activated carbonyl com-
pounds; for examples, see: D. J. Creighton, D. S. Sigman, J. Am. Chem.
Soc. 1971, 93, 6314; S. Shinkai, T. C. Bruice, J. Am. Chem. Soc. 1992,
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[25] O. Kleifeld, A. Frenkel, O. Bogin, M. Eisenstein, V. Brumfeld, Y.
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[26] N. St. Clair, Y.-F Wang, A. L. Margolin, Angew. Chem. 2000, 112, 388;
Angew. Chem. Int. Ed. 2000, 39, 380.
Control Experiments: No chiral alcohol product was formed in the absence
of the HLADH enzyme, while no ketone was reduced to alcohol in the
presence of the model cofactors 1 and 4. The latter result shows that 1 and 4
preferentially bind to the Cp*Rh center in the presence of the ketone, and
they are reduced regioselectively to their 1,4-NADH derivatives 3 and 5, all
in the absence of HLADH.
General Procedure (Oxidation): NAD (83.58 Â 10À3 mmol) or NAD
models 1 or 4 and HLADH (10 units) were placed in a 10-mL Schlenk
flask, and Schlenk techniques were used to deoxygenate the solid mixture.
Under positive argon pressure, potassium phosphate buffer (5 mL, 100 mm,
pH 7.04, deoxygenated) and (S)-2-pentanol (83.58 Â 10À3 mmol) were
added successively through a syringe. The reaction flask was immediately
capped securely with a glass stopper and shaken by using a shaker at room
temperature. The progress of the reaction was monitored by means of GC,
and the product, 2-pentanone, was identified by comparing the retention
time with that of an authentic sample. The oxidation of (R)-2-pentanol was
also tested under the same conditions, and its reaction rate was found to be
much slower than that of (S)-2-pentanol. The relative rates of (S)- and (R)-
2-pentanol in the first 24 hr were ꢀ4:1. Additionally, the reactions were
found to reach equilibrium after ꢀ60 h (in the case of (S)-2-pentanol), at
which point both 2-pentanol and 2-pentanone were present in the reaction
mixture in a ratio of ꢀ40:60. The same procedure described in the example
[27] R. H. Fish, J. B. Kerr, H. C. Lo, US Patent Pending. Preliminary
report, Abstract Paper 219th National ACS meeting (San Francisco,
CA), 2000, INORG 660.
Transfer of Chiral Information through Achiral
Ion Recognition by a Novel Pseudocrown Ether
with a Binaphthyl Moiety
with NAD was followed with the water soluble model 4. Both racemic
2-pentanol and (S)-2-pentanol were tested, and similar results were
Tatsuya Nabeshima,* Akihiro Hashiguchi,
Toshiyuki Saiki, and Shigehisa Akine
obtained as stated in the case of NAD , except that the reaction rate
became slower after 24 h.
Chiral products obtained from metabolic processes are
often used as reactants for subsequent asymmetric reactions
in different chiral environments.[1] Not only chemical reac-
tions but also physical events, such as the selective transport of
chiral substrates, require chiral communication between the
molecules engaged in the chiral process. Thus, transfer,
transduction, modulation, and amplification of chiral infor-
mation are essential issues for all chiral phenomena. These
processes, however, are usually regulated by chiral molecules.
Hence, the regulation of such chiral events by an achiral
species is extremely fascinating and important.
Received: September 5, 2001 [Z17856]
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Allostery and feedback are good examples of the transfer of
molecular information, and they regulate many biological
events that are linked to each other.[2] These regulating
processes play an important role in controlling the function of
proteins and they are effective for triggering a certain cascade
of reactions in which molecular information is transferred
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recently been reported in which their function is regulated by
a single effector, although multistep response to several
different stimuli should be very useful for constructing
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[7] E. Steckhan, S. Herrmann, R. Ruppert, E. Dietz, M. Frede, E. Spika,
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[13] H. C. Lo, O. Buriez, J. B. Kerr, R. H. Fish, Angew. Chem. 1999, 111,
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[14] H. C. Lo, C. Leiva, O. Buriez, J. B. Kerr, M. M. Olmstead, R. H. Fish,
Inorg. Chem. 2001, 40, 6705.
Here we report that podand 1[6] dually responds to external
stimuli, its conversion to a pseudocrown ether complex
[CuI(1)], and the transfer of chiral information in [CuI(1)]
by achiral guests, namely alkali metal ions. Precursor
[15] S. J. Burton, C. V. Stead, R. J. Ansell, C. R. Lowe, Enzyme Microb.
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[16] S. Dilmaghanian, C. V. Stead, R. J. Ansell, C. R. Lowe, Enzyme
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[18] H. Ekland, C.-L. Branden, In Biological Macromolecules and
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[19] M. G. Rossmann, A. Liljas, C.-L. Branden, L. J. Banaszak in The
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[21] W. N. Lipscomb, N. Strater, Chem. Rev. 1996, 96, 2375.
[*] Prof. T. Nabeshima, A. Hashiguchi, Dr. T. Saiki, Dr. S. Akine
Department of Chemistry
University of Tsukuba
Tsukuba, Ibaraki 305-8571 (Japan)
Fax : (81)298-53-6503
Supporting information for this article is available on the WWW under
Angew. Chem. Int. Ed. 2002, 41, No. 3
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
1433-7851/02/4103-0481 $ 17.50+.50/0
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