Oriyama, J. Org. Chem., 1999, 64, 4506; (d) H. Kawanami and Y.
Ikushima, Chem. Commun., 2000, 2089; (e) R. J. Sowden, M. F. Sellin,
N. D. Blasio and D. J. Cole-Hamilton, Chem. Commun., 1999, 2511; (f)
T. Mizuno, N. Okamoto, T. Ito and T. Miyata, Tetrahedron Lett., 2000,
41, 1051; (g) M. Kunert, M. Brauer, O. Klobes, H. Gorls and E. Dinjus,
Eur. J. Inorg. Chem., 2000, 1803; (h) Y. Wada, T. Kitamura and S.
Yanagida, Res. Chem. Intermed., 2000, 26, 153; (i) M. Tokuda, T.
Kabuki, Y. Kato and H. Suginome, Tetrahedron Lett., 1995, 36,
3345.
2 B. Zwanenburg, M. Mikolajczyk and P. Kielbasinski, Enzymes in
Action, Kluwer Academic Publishers, Dordrecht, 2000; W.-D. Fessner,
Biocatalysis, From Discovery to Application, Springer-Verlag, Berlin,
2000; K. Faber, Biotransformations, Springer-Verlag, Berlin, 2000; 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.
Fig. 2 Effect of pressure on conversion of pyrrole to pyrrole-2-carboxylate
by the cells.
3 F. C. Hartman and M. R. Harpel, Annu. Rev. Biochem., 1994, 63,
197.
4 B. A. Parkinson and P. F. Weaver, Nature, 1984, 309, 148; M. Kodaka
and Y. Kubota, J. Chem. Soc., Perkin Trans. 2, 1999, 891; R. Obert and
B. C. Dave, J. Am. Chem. Soc., 1999, 121, 12192; S. Kuwabata, R.
Tsuda, K. Nishida and H. Yoneyama, Chem. Lett., 1993, 1631; S.
Kuwabata, R. Tsuda and H. Yoneyama, J. Am. Chem. Soc., 1994, 116,
5437.
critical pressure did not favorably shift the carboxylation
equilibrium.
In a typical experiment, B. megaterium PYR2910 was grown
as previously described.7b To a stainless steel pressure-resistant
vessel containing a magnetic stirrer bar as previously de-
scribed,11 pyrrole (0.40 M, 0.50 mL), potassium phosphate
buffer (pH 5.5, 0.40 M, 0.50 mL), ammonium acetate (0.56 M,
0.50 mL), the cells (OD610 = 32, 0.50 mL) and KHCO3 (0.60
g) were added. The vessel was then warmed to 40 °C, and CO2
preheated to 40 °C was introduced to a final pressure of 10 MPa.
The mixture was stirred at 40 °C for 3 h, and the CO2 was
liquefied at 210 °C and then the gas pressure was released. The
chemical yield was measured by HPLC analysis as previously
described.7b
In conclusion, cells of B. megaterium catalyzed the conver-
sion of pyrrole to pyrrole-2-carboxylate in supercritical CO2 at
40 °C with pressures up to 10 MPa, and a higher yield was
obtained under supercritical conditions than at atmospheric
pressure. This finding will play a significant role both in
investigating enzyme species suitable for the biocatalysis in
supercritical CO2 and in developing synthetic methods utilizing
CO2.
5 K. Sugimura, S. Kuwabata and H. Yoneyama, J. Am. Chem. Soc., 1989,
111, 2361.
6 K. Sugimura, S. Kuwabata and H. Yoneyama, J. Electroanal. Chem.,
1990, 299, 241.
7 (a) M. Wieser, T. Yoshida and T. Nagasawa, Tetrahedron Lett., 1998,
39, 4309; (b) M. Wieser, N. Fujii, T. Yoshida and T. Nagasawa, Eur. J.
Biochem., 1998, 257, 495; (c) T. Yoshida and T. Nagasawa, J. Biosci.
Bioeng., 2000, 89, 111; (d) M. Wieser, T. Yoshida and T. Nagasawa, J.
Mol. Catal. B: Enzymatic, 2001, 11, 179.
8 Z. He and J. Wiegel, Eur. J. Biochem., 1995, 229, 77; Z. He and J.
Wiegel, J. Bacteriol., 1996, 178, 3539.
9 A. J. Mesiano, E. J. Beckman and A. J. Russell, Chem. Rev., 1999, 99,
623; Y. Ikushima, Adv. Colloid Interface Sci., 1997, 71–72, 259; E.
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; A. M.
Klibanov, Nature, 2001, 409, 241; S. V. Kamat, E. J. Beckman and A.
J. Russell, J. Am. Chem. Soc., 1993, 115, 8845; O. Aaltonen and M.
Rantakylä, Chemtech, 1991, 240; S.-H. Yoon, H. Nakaya, O. Ito, O.
Miyawaki, K.-H. Park and K. Nakamura, Biosci. Biotechnol. Biochem.,
1998, 62, 170.
10 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.
11 T. Matsuda, T. Harada and K. Nakamura, Chem. Commun., 2000,
1367.
This work was supported by a Grant-in-Aid from the Taisho
Pharmaceutical Co. Award in Synthetic Organic Chemistry,
Japan, the Sasakawa Scientific Research Grant from the Japan
Science Society, 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 Culture of Japan.
12 T. Mori and Y. Okahata, Chem. Commun., 1998, 2215; T. Mori, A.
Kobayashi and Y. Okahata, Chem. Lett., 1998, 921.
13 Control reaction using inactivated cells of B. Megaterium [inactivation
conditions: 90 °C, 2 h, reaction conditions: 10 MPa, 40 °C, 3 h, cells: 1.0
mL (OD610 = 32)] afforded no carboxylation product, which indicates
that a biocatalyst is at work and that the carboxylation is not an
unexpected process promoted by non-enzymic constituents of the
cell.
Notes and references
1 (a) P. G. Jessop, T. Ikariya and R. Noyori, Chem. Rev., 1999, 99, 475;
(b) M. Yoshida, N. Hara and S. Okuyama, Chem. Commun., 2000, 151;
(c) T. Sakakura, J.-C. Choi, Y. Saito, T. Masuda, T. Sako and T.
Chem. Commun., 2001, 2194–2195
2195