Table 1 Reduction of various ketones by immobilized cell in scCO
2
Osaka University and Professor Hori and Dr Tabata at Fukui
University. This work was supported by a Grant-in-Aid for
Encouragement of Young Scientists (No. 12740400) and a
Grant-in-Aid for Scientific Research (C) (No. 11640602) from
the Ministry of Education, Science, Sports and Cultre of Japan.
The authors are grateful to Osaka Yuki Kagaku Kogyo Co., Ltd.
for providing BL-100® (water-absorbing polymer).
Notes and references
1
A. J. Mesiano, E. J. Beckman and A. J. Russell, Chem. Rev., 1999, 99,
23; Y. Ikushima, Adv. Colloid Interface Sci., 1997, 71–72, 259; E.
6
Cernia and C. Palocci, in Methods in Enzymology, ed. J. N. Abelson and
M. I. Simon, Academic Press, San Diego, 1997 , vol. 286, p. 495; S. V.
Kamat, E. J. Beckman and A. J. Russell, Crit. Rev. Biotechnol., 1995,
1
5, 41; O. Aaltonen and M. Rantakyl a¨ , CHEMTECH, 1991, 240; P. G.
Jessop, T. Ikariya and R. Noyori, Chem. Rev., 1999, 99, 475; A. Baiker,
Chem. Rev., 1999, 99, 453; J. F. Brennecke and J. E. Chateauneuf,
Chem. Rev., 1999, 99, 433; T. Moriyoshi, T. Kita and Y. Uosaki, Ber.
Bunsenges. Phys. Chem., 1993, 97, 589.
2
S.-H. Yoon, H. Nakaya, O. Ito, O. Miyawaki, K.-H. Park and K.
Nakamura, Biosci. Biotechnol. Biochem., 1998, 62, 170; S. H. Yoon, O.
Miyawaki, K.-H. Park and K. Nakamura, J. Ferment. Bioeng., 1996, 82,
3
1
1
34; Y. Ikushima, N. Saito, M. Arai and H. W. Blanch, J. Phys. Chem.,
995, 99, 8941; J. C. Erickson, P. Schyns and C. L. Cooney, AIChE J.,
990, 36, 299; N. Fontes, M. C. Almeida, C. Peres, S. Garcia, J. Grave,
M. R. Aires-Barros, C. M. Soares, J. M. S. Cabral, C. D. Maycock and
S. Barreiros, Ind. Eng. Chem. Res., 1998, 37, 3189; N. Fontes, E.
Nogueiro, A. M. Elvas, T. C. d. Sampaio and S. Barreiros, Biochim.
Biophys. Acta, 1998, 1383, 165.
3
4
5
6
7
T. W. Randolph, H. W. Blanch, J. M. Prausnitz and C. R. Wilke,
Biotechnol. Lett., 1985, 7, 325.
D. A. Hammond, M. Karel, A. M. Klibanov and V. J. Krukonis, Appl.
Biochem. Biotechnol., 1985, 11, 393.
K. Nakamura, Y. M. Chi, Y. Yamada and T. Yano, Chem. Eng.
Commun., 1986, 45, 207.
T. Mori and Y. Okahata, Chem. Commun., 1998, 2215; T. Mori, A.
Kobayashi and Y. Okahata, Chem. Lett., 1998, 921.
S. Kamat, J. Barrera, E. J. Beckman and A. J. Russell, Biotechnol.
Bioeng., 1992, 40, 158; S. V. Kamat, B. Iwaskewycz, E. J. Beckman and
A. J. Russell, Proc. Natl. Acad. Sci. USA, 1993, 90, 2940; S. V. Kamat,
E. J. Beckman and A. J. Russell, J. Am. Chem. Soc., 1993, 115, 8845;
A. K. Chaudhary, S. V. Kamat, E. J. Beckman, D. Nurok, R. M. Kleyle,
P. Hajdu and A. J. Russell, J. Am. Chem. Soc., 1996, 118, 12 891.
released. The resulting residue was dissolved in ether, and the
mixture was put on Extrelut and quickly eluted with ether.
Chemical yield and ee were measured using a chiral GC-column
8 T. W. Randolph, D. S. Clark, H. W. Blanch and J. M. Prausnitz, Science,
1988, 239, 387; T. W. Randolph, H. W. Blanch and J. M. Prausnitz,
AIChE J., 1988, 34, 1354.
9 (a) R. Azerad and D. Buisson, in Microbial Reagents in Organic
Synthesis, NATO ASI Series C, ed. S. Servi, Kluwer Academic
Publishers, Dordrecht, 1992, p. 421; (b) T. Matsuda, T. Harada, N.
Nakajima, T. Itoh and K. Nakamura, J. Org. Chem., 2000, 65, 157; (c)
K. Nakamura, Y. Inoue, T. Matsuda and I. Misawa, J. Chem. Soc.,
Perkin Trans. 1, 1999, 2397; (d) K. Nakamura and T. Matsuda, J. Org.
Chem., 1998, 63, 8957.
2
1
(
Chirasil-DEX CB; 25 m; He 2 mL min ). The absolute
configurations were determined by comparing the GC retention
times with those of authentic samples.
In conclusion, the alcohol dehydrogenase from G. candidum
was found to be active in scCO at 35 °C and 10 MPa and to
2
catalyze asymmetric reduction of various ketones with excellent
enantioselectivities. For practical use, there has so far been
some hesitation to use alcohol dehydrogenases in spite of their
high enantioselectivities because of the difficulties in extracting
the product from aqueous solvents. We believe that this report
opens up new possibilities for asymmetric reduction by an
enzyme with a natural and easily-removable solvent.
The authors greatly appreciate the advice and technical
2
support in assembling the scCO reactor given by Professor
Okamoto at Kyoto Institute of Technology, Professor Okahata
and Dr Mori at Tokyo Institute of Technology, Dr Ozaki at
10 The reaction was stopped as soon as the pressure reached 10 MPa by
cooling at 210 °C, then a negligible amount of the reaction proceeded
(
yield 5%), which was probably due to the reaction during the time
between the critical pressure and 10 MPa.
1
1 S. M. Roberts, J. Chem. Soc., Perkin Trans. 1, 2000, 611; S. M. Roberts,
J. Chem. Soc., Perkin Trans. 1, 1999, 1; S. M. Roberts, J. Chem. Soc.,
Perkin Trans. 1, 1998, 157; T. Benincori, E. Cesarotti, O. Piccolo and F.
Sannicolo, J. Org. Chem., 2000, 65, 2043; Y.-J. Cherng, J.-M. Fang and
T.-J. Lu, J. Org. Chem., 1999, 64, 3207; T. Ohkuma, M. Koizumi, H.
Doucet, T. Pham, M. Kozawa, K. Murata, E. Katayama, T. Yokozawa,
T. Ikariya and R. Noyori, J. Am. Chem. Soc., 1998, 120, 13529.
1368
Chem. Commun., 2000, 1367–1368